Method for manufacturing laminate and method for manufacturing semiconductor element

Abstract

This method for manufacturing a laminate having a surface modified layer and a semiconductor substrate comprises: a first step for applying a surface modifier containing an organic compound (A) having a hydroxy group which may be protected by a deprotectable protecting group and a solvent (B) onto the semiconductor substrate, and thereafter firing the surface modifier to obtain a surface modified layer precursor; and a second step for bringing the surface modified layer precursor into contact with a thinning liquid (X) to thin the surface modified layer precursor to obtain the surface modified layer having a film thickness of 5 nm or less.

Description

Method for manufacturing laminate and method for manufacturing semiconductor element

[0001] The present invention relates to a method for manufacturing a laminate, preferably a method for manufacturing a laminate on which a resist pattern is formed, and also to a method for manufacturing a semiconductor element.

[0002] Lithography processes using resist compositions have been conventionally performed in the manufacture of semiconductor devices. In recent years, with the increasing integration of semiconductor devices, there has been a demand for finer patterns, such as wiring. As patterns become finer, light sources with shorter wavelengths, such as far ultraviolet light, vacuum ultraviolet light, electron beams (EB), and X-rays, have begun to be used. In particular, short-wavelength light such as KrF excimer lasers (wavelength 248 nm) and ArF excimer lasers (wavelength 193 nm), have recently been used to form resist patterns.

[0003] Accordingly, the effects of diffuse reflection and standing waves of actinic rays from semiconductor substrates have become a major problem, and therefore, in order to solve this problem, a method of providing an anti-reflective coating (Bottom Anti-Reflective Coating: BARC) between the resist and the semiconductor substrate has been widely studied. As such an anti-reflective coating, many studies have been conducted on organic anti-reflective coatings formed from compositions containing polymers having light-absorbing groups (chromophores) because of their ease of use (for example, Patent Document 1).

[0004] On the other hand, with EUV (extreme ultraviolet, wavelength 13.5 nm) and electron beams, which are applied to further fine processing techniques, the problem of reflection from semiconductor substrates does not arise, but resist pattern collapse associated with pattern miniaturization becomes a problem, and therefore, resist underlayer films with high adhesion to resists are being investigated.

[0005] Special Publication No. 2008-501985

[0006] Conventional resist underlayer films have the problem of being prone to side etching and other etching defects during the etching process. Therefore, if it were possible to modify the substrate surface using a surface modification layer that is thinner than conventional underlayer films, it would be expected that this would improve photoresist adhesion without causing side etching and other etching defects, and thereby improve photoresist resolution in advanced lithography processes. However, it is not easy to form a thin surface modification layer uniformly.

[0007] The present invention has been made in consideration of such circumstances, and aims to provide a method for manufacturing a laminate capable of forming a thin surface modification layer, a method for manufacturing a semiconductor element using the manufacturing method, and a laminate having a thin surface modification layer.

[0008] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0009] That is, the present invention encompasses the following: [1] A method for producing a laminate having a surface-modified layer and a semiconductor substrate, comprising: a first step of applying a surface-modified agent containing an organic compound (A) having a hydroxy group optionally protected by a deprotectable protecting group and a solvent (B) onto a semiconductor substrate, followed by baking the applied surface-modified layer precursor; and a second step of contacting the surface-modified layer precursor with a thinning liquid (X) to thin the surface-modified layer precursor, thereby obtaining a surface-modified layer having a film thickness of 5 nm or less. [2] The method for producing a laminate according to [1], wherein the organic compound (A) is any one of: a vinyl polymer (A1) having a hydroxy group; a polymer (A2) having a unit structure represented by the following formula (Y); a resin (A3) having a complex unit structure, wherein the complex unit structure has a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms, and is obtained by a reaction to form a covalent bond between a carbon atom constituting the aromatic ring of the unit structure (A) and a carbon atom in the unit structure (B); a polymer (A4) having a unit structure represented by the following formula (Z1); and a compound (A5) having two or more of the following structures (M). (In formula (Y), T represents a divalent group having an aliphatic ring. Q represents a divalent organic group having a hydroxy group, and T and R １１ R represents a divalent organic group connecting １１ represents a monovalent group. In formula (Z1), A's each independently represent a hydrogen atom, a methyl group, or an ethyl group; １ and Q ２ represent each independently a divalent group. (In structure (M), R １０１represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bond.) [3] The method for producing a laminate according to [1] or [2], wherein the solvent (B) contains at least one selected from the group consisting of a carboxylic acid having a hydroxy group, a linear or cyclic alkyl ketone, a cyclic lactone, an alkylene glycol monoalkyl ether, a monocarboxylic acid ester of an alkylene glycol monoalkyl ether, and an alkoxycarboxylic acid ester of an alkylene glycol monoalkyl ether. [4] The method for producing a laminate according to any of [1] to [3], wherein the thinning liquid (X) contains at least one of an organic solvent and water. [5] The method for producing a laminate according to any of [1] to [4], wherein the surface modifier further contains at least one compound (C) selected from the group consisting of an acid, a salt thereof, and an acid generator. [6] The method for producing a laminate according to any of [1] to [5], wherein the semiconductor substrate is an inorganic or organic substrate, or a substrate having an inorganic or organic film. [7] The method for producing a laminate according to [6], wherein the inorganic material is at least one selected from the group consisting of metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxycarbides, and metal carbonitrides. [8] The method for producing a laminate according to [6], wherein the organic material is at least one selected from the group consisting of amorphous carbon, graphite, fullerenes, carbon nanotubes, diamond, diamond-like carbon, polyimides, and organic films doped or partially substituted with boron, oxygen, nitrogen, phosphorus, silicon, sulfur, or a halogen. [9] The method for producing a laminate according to any one of [1] to [8], wherein the laminate further comprises a resist underlayer film.

[10] The method for producing a laminate according to any one of [1] to [9], wherein the second step is a step of spin-coating the thinning solution (X) on the surface-modified layer precursor to thin the surface-modified layer precursor to obtain a surface-modified layer having a thickness of 5 nm or less.

[11] The method for producing a laminate according to any one of [1] to

[10] , wherein the laminate is used for EUV or electron beam lithography.

[12] A method for manufacturing a semiconductor element, comprising the steps of forming a resist film on a laminate obtained by the method for manufacturing a laminate according to any one of [1] to

[11] , and exposing and developing the resist film to obtain a resist pattern.

[13] A laminate having a semiconductor substrate and a surface-modified layer having a thickness of 5 nm or less, formed using a surface modifier containing an organic compound (A) having a hydroxy group which may be protected by a deprotectable protecting group and a solvent (B).

[14] The laminate according to

[13] , which is used for EUV or electron beam lithography.

[15] A surface modifier containing an organic compound (A) having a hydroxy group which may be protected by a deprotectable protecting group and a solvent (B), which is used in the method for manufacturing a laminate according to any one of [1] to

[11] .

[0010] According to the present invention, it is possible to provide a method for manufacturing a laminate capable of forming a thin surface-modified layer, a method for manufacturing a semiconductor element using the manufacturing method, and a laminate having a thin surface-modified layer.

[0011] (Method for producing a laminate, and laminate) The method for producing a laminate of the present invention includes a first step and a second step. The method for producing a laminate of the present invention may further include other steps. The first step is a step of applying a surface modifier containing an organic compound (A) having a hydroxy group that may be protected by a deprotectable protecting group and a solvent (B) to a semiconductor substrate, followed by baking to obtain a surface modified layer precursor. The second step is a step of thinning the surface modified layer precursor by contacting the surface modified layer precursor with a thinning liquid (X) to obtain a surface modified layer with a film thickness of 5 nm or less. An organic film is obtained by applying a surface modifier containing an organic compound (A) having a hydroxy group that may be protected by a deprotectable protecting group and a solvent (B) and then baking. However, it is not easy to obtain a thin film (for example, a film with a film thickness of 5 nm or less) without film defects such as pinholes or coating unevenness through this step alone, and it is necessary to thoroughly control the coating conditions, baking conditions, etc. Therefore, the present inventors have intensively studied methods for producing laminates capable of forming thin surface-modified layers, and have found that a thin surface-modified layer can be formed by forming a layer (surface-modified layer precursor) with a thickness greater than the target thickness in the first step, and then contacting the layer with a thinning liquid (X) to thin the layer in the second step, thereby arriving at the present invention. When the surface-modified layer precursor obtained from the surface modifier is contacted with the thinning liquid (X), the surface-modified layer precursor is not completely removed from the substrate, but remains on the substrate as a thin surface-modified layer. The present inventors believe that this is related to the interaction of the hydroxyl group, which may be protected by a deprotectable protecting group, possessed by the organic compound (A) with the substrate.

[0012] The laminate obtained by the laminate manufacturing method of the present invention has a surface modification layer and a semiconductor substrate.

[0013] The laminate obtained by the laminate manufacturing method of the present invention is suitable for use in EUV (extreme ultraviolet, wavelength 13.5 nm) or electron beam lithography. The laminate obtained by the laminate manufacturing method of the present invention may further comprise other layers or films. Examples of such other layers include a resist underlayer film. The resist underlayer film is not particularly limited as long as it is a resist underlayer film used in a lithography process. The resist underlayer film may be, for example, a silicon-containing resist underlayer film or an organic underlayer film. Examples of the organic underlayer film include an organic underlayer film having a high carbon content. An organic underlayer film having a high carbon content can be obtained, for example, from a composition containing a novolac resin in the broad sense. Examples of such compositions include the resist underlayer film-forming compositions described in WO 2010 / 147155, WO 2012 / 077640, WO 2013 / 005797, and WO 2017 / 094780. The resist underlayer film is, for example, a layer below the surface modification layer. The resist underlayer film is, for example, disposed between the semiconductor substrate and the surface modification layer. In the present invention, there is no clear distinction between a film and a layer.

[0014] The thickness of the surface modification layer is 5 nm or less, preferably 3 nm or less. There is no particular limitation on the lower limit of the thickness of the surface modification layer, and the thickness of the surface modification layer may be 0.1 nm or more, or 0.2 nm or more.

[0015] In the present invention, the film thickness is measured as follows: The film thickness is measured using an ellipsometric film thickness measuring device RE-3100 (manufactured by SCREEN).

[0016] <First Step> The first step is a step of obtaining a surface modification layer precursor. In the first step, a surface modification agent is applied onto a semiconductor substrate, and then the surface modification layer precursor is obtained by baking.

[0017] The semiconductor substrate used in the first step is not particularly limited as long as it is a substrate used in the manufacture of precision integrated circuit devices, and examples of the semiconductor substrate include inorganic substrates, organic substrates, substrates having an inorganic film, and substrates having an organic film.

[0018] Examples of inorganic substances include arsenic, metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxycarbides, and metal carbonitrides. These may be used alone or in combination of two or more. Examples of metals include silicon, germanium, titanium, tungsten, hafnium, zirconium, chromium, copper, aluminum, indium, gallium, palladium, iron, tantalum, iridium, molybdenum, and alloys thereof. Examples of metal oxides include SiO ２ , TiO ２ Examples of metal nitrides include SiN, TiN, and TaN. Examples of metal carbides include SiC and TiC. Examples of metal oxynitrides include SiON and TiON. Examples of metal oxycarbides include SiOC and TiOC. Examples of metal carbonitrides include SiCN and TiCN.

[0019] Examples of organic materials include amorphous carbon, graphite, fullerene, carbon nanotubes, diamond, diamond-like carbon, and polyimide. These materials can be used alone or in combination of two or more. The organic materials described above may be doped or partially substituted with boron, oxygen, nitrogen, phosphorus, silicon, sulfur, or halogen.

[0020] Examples of the semiconductor substrate include semiconductor substrates such as silicon wafers coated with a silicon oxide film, a silicon nitride film, or a silicon oxynitride film, silicon nitride substrates, quartz substrates, glass substrates (including alkali-free glass, low-alkali glass, and crystallized glass), glass substrates on which an ITO (indium tin oxide) film or an IZO (indium zinc oxide) film is formed, plastic (polyimide, PET, etc.) substrates, substrates coated with low dielectric constant materials (low-k materials), and flexible substrates.

[0021] The method for applying the surface modifier to the semiconductor substrate is not particularly limited, and can be carried out by a suitable application method such as using a spinner or a coater.

[0022] After the surface modifier is applied to the semiconductor substrate, the substrate can be baked using a heating means such as a hot plate. Baking conditions are appropriately selected from a baking temperature of 40°C to 400°C or 80°C to 250°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 120°C to 250°C and the baking time is 0.5 minutes to 2 minutes.

[0023] The baking evaporates the solvent in the surface modifier, yielding a layer-like surface-modified layer precursor. In some cases, the baking also induces a crosslinking reaction, yielding a crosslinked layer. Crosslinking includes partial crosslinking.

[0024] The film thickness of the surface modification layer precursor formed here is, for example, 1 nm to 1,000 nm, or 1 nm to 500 nm, or 1 nm to 300 nm, or 1 nm to 200 nm, or 1 to 150 nm.

[0025] <<Surface Modifier>> The surface modifier contains an organic compound (A) having a hydroxy group that may be protected with a deprotectable protecting group, and a solvent (B). The surface modifier may further contain other components. The surface modifier used in the method for producing the laminate of the present invention is also within the scope of the present invention.

[0026] <<<Organic Compound (A)>>> The organic compound (A) is not particularly limited as long as it has a hydroxy group that may be protected with a deprotectable protecting group, and can be appropriately selected depending on the purpose. The organic compound (A) may be a low molecular weight compound or a high molecular weight compound. The organic compound may be a resin or a polymer.

[0027] The protecting group for a hydroxy group is not particularly limited as long as it is deprotectable, and examples thereof include alkyl groups having 1 to 4 carbon atoms and alkoxyalkyl groups having a total of 2 to 6 carbon atoms. A hydroxy group protected by a deprotectable protecting group is, for example, a hydroxy group in a hydroxymethyl group bonded to a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring. The deprotectable protecting group can be deprotected, for example, by heat. The deprotectable protecting group can be deprotected, for example, in the presence of a catalyst.

[0028] When the organic compound (A) is a resin or a polymer, specific examples thereof include addition polymerization polymers and condensation polymerization polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac, naphthol novolac, polyether, polyamide, and polycarbonate.

[0029] The weight average molecular weight of the organic compound (A) is not particularly limited and can be, for example, 300 to 1,000,000. From the viewpoint of suppressing precipitation in the surface modifier, the weight average molecular weight is preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less, and from the viewpoint of achieving both storage stability and coatability, the weight average molecular weight is preferably 300 or more.

[0030] Examples of the organic compound (A) are given below.

[0031] <<<<<Polymer (A1)>>>> Polymer (A1), an example of the organic compound (A), is a vinyl polymer having a hydroxy group. A vinyl polymer is a polymer formed by polymerizing the polymerizable unsaturated bond of a compound having a group having a polymerizable unsaturated bond. Polymer (A1) may be a homopolymer or a copolymer. Examples of the group having a polymerizable unsaturated bond include a (meth)acryloyl group, a (meth)acrylamide group, a vinyl group, a vinylaryl group (e.g., a styryl group), a vinyloxy group, an allyl group, and a maleimide group.

[0032] The polymer (A1) has, for example, a unit structure represented by the following formula (X1). (In formula (X1), R １ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. １ represents an ester bond, an optionally substituted phenylene group, or an amide bond. ２ represents a monovalent group having a hydroxy group.

[0033] Examples of the unit structure represented by formula (X1) include unit structures represented by the following formulae (X1-1) to (X1-3). (In formulas (X1-1) to (X1-3), R １ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ２ represents a monovalent group having a hydroxy group. ２ each independently represents a substituent; and m represents an integer of 0 to 4.

[0034] R １Examples of the alkyl group having 1 to 10 carbon atoms in the formula (I) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n- propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group , 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples include a 3-trimethylcyclopropyl group, a 1-ethyl-2-methylcyclopropyl group, a 2-ethyl-1-methylcyclopropyl group, a 2-ethyl-2-methylcyclopropyl group, a 2-ethyl-3-methylcyclopropyl group, an n-heptyl group, a cycloheptyl group, a norbornyl group, an n-octyl group, a cyclooctyl group, an n-nonyl group, an isobornyl group, a tricyclononyl group, an n-decyl group, an adamantyl group, and a tricyclodecyl group. Of these, a methyl group is preferred.

[0035] R ２ Examples of the substituent in include a halogen atom, a hydroxy group, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms.

[0036] L ２ The number of hydroxy groups contained in L may be one or two or more. ２ Examples of the hydroxyl group include a hydroxyl group and a monovalent group having 1 to 20 carbon atoms and a hydroxyl group. The monovalent group having 1 to 20 carbon atoms and a hydroxyl group may have only carbon atoms and hydrogen atoms as constituent atoms other than the hydroxyl group. The monovalent group having 1 to 20 carbon atoms and a hydroxyl group may or may not have a heteroatom other than the hydroxyl group. Examples of heteroatoms include an oxygen atom, a nitrogen atom, and a sulfur atom. The monovalent group having 1 to 20 carbon atoms and a hydroxyl group may or may not have a halogen atom. The monovalent group having 1 to 20 carbon atoms and a hydroxyl group may or may not have an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles. Examples of aromatic hydrocarbon rings include a benzene ring and a naphthalene ring.

[0037] Examples of the monomer used to derive the unit structure represented by formula (X1-1) include the following compounds.

[0038] Examples of the monomer used to derive the unit structure represented by formula (X1-2) include the following compounds. (Me represents a methyl group.)

[0039] Examples of the monomer used to derive the unit structure represented by formula (X1-3) include the following compounds.

[0040] Polymer (A1) may have a unit structure other than the unit structure represented by formula (X1). Examples of monomers that can derive such unit structures include, but are not limited to, acrylic acid, methacrylic acid, acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, and acrylonitrile.

[0041] Specific examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, normal hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthrylmethyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 3-acryloxypropyltriethoxysilane, and glycidyl acrylate, but are not limited to these.

[0042] Specific examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, normal hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthrylmethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, bromophenyl methacrylate, and the like, but are not limited to these.

[0043] Specific examples of the acrylamide compound include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthrylacrylamide.

[0044] Specific examples of methacrylamide compounds include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-anthrylmethacrylamide, but are not limited to these.

[0045] Specific examples of vinyl compounds include, but are not limited to, vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetate, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, and vinylanthracene.

[0046] Specific examples of styrene compounds include, but are not limited to, styrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.

[0047] Examples of maleimide compounds include, but are not limited to, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide.

[0048] <<<<<Polymer (A2)>>>> Polymer (A2), which is an example of the organic compound (A), is a polymer having a unit structure represented by the following formula (Y). (In formula (Y), T represents a divalent group having an aliphatic ring. Q represents a divalent organic group having a hydroxy group, and T and R １１ R represents a divalent organic group connecting １１ represents a monovalent group.

[0049] R １１ The -Q group is a substituent on an aliphatic ring. The aliphatic ring is, for example, a ring having 4 to 10 carbon atoms connected in a ring, and preferably a ring having 6 carbon atoms connected in a ring. The aliphatic ring is, for example, a ring having 4 to 10 carbon atoms connected in a ring, and preferably a ring having 6 carbon atoms connected in a ring. １１ In addition to the -Q group, other substituents may be present, such as an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen atom, a nitro group, and an amino group.

[0050] The polymer (A2) is preferably a polymer having a unit structure represented by the following formula (Y1). (In formula (Y1), R １１ represents a monovalent group. １２ represents a hydrogen atom or a methyl group. １３ represents a hydrogen atom or a methyl group.

[0051] R １１ There is no particular limitation on the group, and examples thereof include organic groups having 1 to 20 carbon atoms.

[0052] The polymer (A2) can be obtained, for example, by reacting a polymer having a unit structure represented by the following formula (Y-1) with a compound represented by the following formula (Y-2). (In formula (Y-1), R １２ represents a hydrogen atom or a methyl group. １３represents a hydrogen atom or a methyl group. １１ represents a monovalent group.

[0053] The above reaction can be carried out, for example, in the presence of a catalyst. Examples of the catalyst include quaternary phosphonium salts such as tetrabutylphosphonium bromide and ethyltriphenylphosphonium bromide, and quaternary ammonium salts such as benzyltriethylammonium chloride. The amount of catalyst used can be selected appropriately from the range of 0.1 to 10 mass% based on the total mass of the raw materials used in the reaction. Optimal reaction temperature and time can be selected from the ranges of, for example, 80 to 160°C and 2 to 50 hours.

[0054] R in formula (Y1) and formula (Y-2) １１ is not particularly limited as long as it is a monovalent group. Examples of monovalent groups include monovalent groups having 1 to 20 carbon atoms. Preferred examples of monovalent groups include aromatic groups. Examples of aromatic groups include monocyclic aromatic hydrocarbon groups and fused ring aromatic hydrocarbon groups.

[0055] Examples of polymers having a unit structure represented by formula (Y-1) include a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (trade name: EHPE3150, manufactured by Daicel Chemical Industries, Ltd.), and a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol and 3,4-epoxycyclohexenylmethyl-3,4'-epoxycyclohexenecarboxylate (trade name: EHPE3150CE, manufactured by Daicel Chemical Industries, Ltd.).

[0056] The compound represented by formula (Y-2) is preferably, for example, a fused-ring aromatic carboxylic acid or a monocyclic aromatic carboxylic acid. Examples of the fused-ring aromatic carboxylic acid include naphthalenecarboxylic acid and anthracenecarboxylic acid, with 9-anthracenecarboxylic acid being preferred. Examples of the monocyclic aromatic carboxylic acid include benzoic acid.

[0057] Examples of the polymer (A2) include polymers having a unit structure represented by the following formula (Y1-1) to polymers having a unit structure represented by the following formula (Y1-12).

[0058] <<<<<Resin (A3)>>>> Resin (A3), an example of organic compound (A), is a resin having a complex unit structure. The complex unit structure has a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms. Resin (A3) is a resin obtained by a reaction that forms a covalent bond between a carbon atom constituting the aromatic ring of unit structure (A) and a carbon atom in unit structure (B). Hereinafter, resin (A3) may be referred to as resin (G). In this specification, resin (G) may be referred to as a "novolac resin."

[0059] The unit structure (A) has a skeleton having an aromatic ring, and the skeleton having an aromatic ring is a phenol skeleton.

[0060] The unit structure (A) has, for example, at least one of an oxygen atom constituting an aromatic ring, a sulfur atom constituting an aromatic ring, an oxygen atom bonded to an aromatic ring, a nitrogen atom constituting an aromatic ring, and a nitrogen atom bonded to an aromatic ring. The unit structure (A) does not have a heteroatom, for example, as an atom constituting an aromatic ring or an atom bonded to an aromatic ring.

[0061] The unit structure (B) is a unit structure derived from an aldehyde compound or an aldehyde equivalent.

[0062] The unit structure (A) has, for example, at least one of an oxygen atom constituting an aromatic ring, a sulfur atom constituting an aromatic ring, an oxygen atom bonded to an aromatic ring, a nitrogen atom constituting an aromatic ring, and a nitrogen atom bonded to an aromatic ring. The unit structure (A) does not have a heteroatom, for example, as an atom constituting an aromatic ring or an atom bonded to an aromatic ring.

[0063] The unit structure (B) is, for example, a unit structure derived from an aldehyde compound or an aldehyde equivalent. The aldehyde equivalent is an organic compound capable of forming a covalent bond with an aromatic ring, and is an organic compound having a ketone group, an acetal group, a ketal group, a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom, a hydroxyl group, an alkoxy group or a halo group bonded to the α-carbon atom of an alkylaryl group, or a carbon-carbon unsaturated bond.

[0064] [I. Definitions of Terms] In this specification, definitions of main terms related to the novolac resin, which is one embodiment of the present invention, are explained below. Unless otherwise specified, the following definitions of each term apply to the novolac resin.

[0065] (I-1) "Novolac Resin" The term "novolac resin" is used in a broad sense to encompass not only phenol-formaldehyde resins (so-called novolac phenolic resins) and aniline-formaldehyde resins (so-called novolac aniline resins) in the narrow sense, but also resins formed by forming a covalent bond (substitution reaction, addition reaction, condensation reaction, addition-condensation reaction, etc.) between an organic compound having a functional group capable of forming a covalent bond with an aromatic ring (for example, an aldehyde group; a ketone group; an acetal group; a ketal group; a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom; a hydroxyl group, an alkoxy group, or a halo group bonded to the α-carbon atom (e.g., the benzylic carbon atom) of an alkylaryl group; or a carbon-carbon unsaturated bond such as in divinylbenzene or dicyclopentadiene) in the presence of an acid catalyst or under equivalent reaction conditions, and an aromatic ring in a compound having an aromatic ring (preferably having heteroatoms such as oxygen, nitrogen, and sulfur atoms as atoms constituting the aromatic ring or atoms bonded to the aromatic ring)

[0066] Therefore, the novolak resin referred to in this specification is a resin formed by linking a plurality of compounds having aromatic rings together, with an organic compound containing a carbon atom derived from the functional group (sometimes referred to as a "linking carbon atom") forming a covalent bond with an aromatic ring in a compound having an aromatic ring via the linking carbon atom.

[0067] In this specification, the terms unit structure (A) and unit structure (B) are used to refer to unit structures constituting a "novolac resin." Unit structure (A) is a unit structure derived from a compound having an aromatic ring. Unit structure (B) is a unit structure derived from a compound having a functional group that enables covalent bonding with the aromatic ring of unit structure (A).

[0068] (I-2) "Residue" A "residue" refers to an organic group in which a hydrogen atom bonded to a carbon atom or a heteroatom (such as a nitrogen atom, oxygen atom, or sulfur atom) is replaced with a bond, and may be a monovalent group or a polyvalent group. For example, replacing one hydrogen atom with one bond results in a monovalent organic group, and replacing two hydrogen atoms with bonds results in a divalent organic group.

[0069] (I-3) "Aromatic Ring" (Aromatic Group, Aryl Group, Arylene Group) The term "aromatic ring" refers to a concept that encompasses aromatic hydrocarbon rings, aromatic heterocycles, and residues thereof [sometimes referred to as "aromatic groups," "aryl groups" (in the case of monovalent groups), or "arylene groups" (in the case of divalent groups)], and encompasses not only monocyclic (aromatic monocycles) but also polycyclic (aromatic polycycles). In the case of polycycles, at least one monocycle is an aromatic monocycle, and the remaining monocycles that form a fused ring with the aromatic monocycle may be a monocyclic heterocycle (heteromonocycle) or a monocyclic alicyclic hydrocarbon (alicyclic monocycle). In this specification, heteroaryl groups are included in the aryl group. Heteroarylene groups are included in the arylene group.

[0070] Examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, indene, naphthalene, azulene, styrene, toluene, xylene, mesitylene, cumene, anthracene, phenanthrene, triphenylene, benzanthracene, pyrene, chrysene, fluorene, biphenyl, corannulene, perylene, fluoranthene, benzo[k]fluoranthene, benzo[b]fluoranthene, benzo[ghi]perylene, coronene, dibenzo[g,p]chrysene, acenaphthylene, acenaphthene, naphthacene, pentacene, and cyclooctatetraene, more typically aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and pyrene; and aromatic hydrocarbon rings such as furan, pyran, pyridine, pyrimidine, pyrazine, thiophene, and pyrrolidone. aromatic heterocycles such as indole, N-alkylpyrrole, N-arylpyrrole, imidazole, pyridine, pyrimidine, pyrazine, triazine, thiazole, indole, phenylindole, bisindolefluorene, bisindolebenzofluorene, bisindoledibenzofluorene, purine, quinoline, isoquinoline, chromene, thianthrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole, and indolocarbazole, and more typically, furan, thiophene, pyrrole, indole, phenylindole, bisindolefluorene, phenothiazine, carbazole, and indolocarbazole, but are not limited thereto.

[0071] The aromatic ring (for example, a benzene ring, a naphthalene ring, etc.) may have an optional substituent, and examples of such a substituent include the following atoms and groups: a halogen atom; a saturated or unsaturated, linear, branched, or cyclic hydrocarbon group (-R ａ ) (including alkyl groups, alkenyl groups, and alkynyl groups (e.g., propargyl groups), and aryl groups, whose hydrocarbon chains may be interrupted one or more times by oxygen atoms), -OR (wherein R is the hydrocarbon group -R ａ ) Aryloxy group -NH ２ , —NHR or —NR ２(Two R's may be the same or different from each other), where R's are the hydrocarbon groups -R ａ - Hydroxyl group - Hydroxyalkyl group - Carboxyl group - Formyl group - Cyano group - Nitro group - Ester group (for example, -CO ２ R or -OCOR, where R is the hydrocarbon group -R ａ an amide group [for example, —NHCOR, —CONHR, —NRCOR (wherein the two Rs may be the same or different), or —CONR ２ (Two R's may be the same or different from each other), where R's are the hydrocarbon groups -R ａ a sulfonyl-containing group (e.g., —SO ２ R, where R is the hydrocarbon group -R ａ or a hydroxyl group -OH.) a thiol group (-SH) a sulfide-containing group (-SR, where R is the hydrocarbon group -R ａ represents an organic group containing an ether bond [R １１ -O-R １１ (R １１ each independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, or an aryl group, such as a phenyl group, a naphthyl group, an anthranyl group or a pyrenyl group; a residue of an ether compound represented by the formula (I); an organic group containing an ether bond, such as a methoxy group, an ethoxy group or a phenoxy group]

[0072] The term "aromatic ring" also includes organic groups having one or more fused rings of aromatic rings (such as benzene, naphthalene, anthracene, and pyrene) with one or more fused aliphatic or heterocyclic rings. Examples of the aliphatic rings include cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclohexane, methylcyclohexene, cycloheptane, and cycloheptene. Examples of the heterocyclic rings include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, and morpholine.

[0073] The "aromatic ring" may be an organic group having a structure in which two or more aromatic rings are linked by a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, and -SO ２ The divalent linking group may also be a divalent group in which one hydrogen atom has been removed from any of the substituents of the aromatic rings described above.

[0074] (I-4) "Heterocycle" The term "heterocycle" encompasses both aliphatic heterocycles and aromatic heterocycles, and is a concept that encompasses not only monocyclic (heteromonocyclic) but also polycyclic (heteropolycyclic). In the case of a polycyclic, at least one monocyclic ring is a heteromonocyclic ring, but the remaining monocyclic rings may be aromatic hydrocarbon monocyclic or alicyclic monocyclic. For the aromatic heterocycle, the examples in (I-3) above can be referred to. As with the aromatic ring in (I-3) above, it may have a substituent.

[0075] (I-5) "Non-aromatic ring" (aliphatic ring) When the "non-aromatic ring" is a monocycle, the "non-aromatic monocycle" refers to a monocyclic hydrocarbon that does not belong to the aromatic group, and is typically a monocycle of an alicyclic compound. It may also be called an aliphatic monocycle (which may include an aliphatic heteromonocycle, or may contain an unsaturated bond as long as it does not belong to the aromatic compound). As with the aromatic ring of (I-3) above, it may have a substituent.

[0076] Examples of non-aromatic monocyclic rings (aliphatic rings, aliphatic monocyclic rings) include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, cyclohexene, methylcyclohexene, cycloheptane, and cycloheptene.

[0077] When the "non-aromatic ring" is a polycyclic ring, the "non-aromatic polycyclic ring" refers to a polycyclic hydrocarbon that does not belong to the aromatic group, and is typically a polycyclic ring of an alicyclic compound. It may also be called an aliphatic polycyclic ring (which may include an aliphatic heteropolycyclic ring (at least one of the monocyclic rings constituting the polycyclic ring is an aliphatic heterocyclic ring), or may contain an unsaturated bond as long as it does not belong to the aromatic compound). It includes a non-aromatic bicyclic ring, a non-aromatic tricyclic ring, and a non-aromatic tetracyclic ring.

[0078] When the "non-aromatic ring" is a bicycle, the "non-aromatic bicycle" refers to a fused ring composed of two monocyclic hydrocarbons that are not aromatic, and is typically a fused ring of two alicyclic compounds. In this specification, it may also be referred to as an aliphatic bicycle (which may include an aliphatic heterobicycle, and may contain unsaturated bonds as long as it does not belong to the aromatic compound). Examples of non-aromatic bicycles include bicyclopentane, bicyclooctane, and bicycloheptene.

[0079] When the "non-aromatic ring" is a tricycle, the "non-aromatic tricycle" refers to a fused ring composed of three monocyclic hydrocarbons that are not aromatic, and is typically a fused ring of three alicyclic compounds (each of which may be a heterocycle or may contain an unsaturated bond as long as it is not an aromatic compound). Examples of non-aromatic tricycles include tricyclooctane, tricyclononane, and tricyclodecane.

[0080] When the "non-aromatic ring" is a tetracyclic ring, the "non-aromatic tetracyclic ring" refers to a fused ring composed of four monocyclic hydrocarbons that are not aromatic, and is typically a fused ring of four alicyclic compounds (each of which may be a heterocyclic ring or may contain an unsaturated bond as long as it is not an aromatic compound). Examples of non-aromatic tetracyclic rings include hexadecahydropyrene.

[0081] (I-6) The term "carbon atoms constituting a ring (moiety)" refers to the carbon atoms constituting a hydrocarbon ring (which may be an aromatic ring, an aliphatic ring, or a heterocyclic ring) in an unsubstituted state.

[0082] (I-7) The term "hydrocarbon group" refers to a group formed by removing one or more hydrogen atoms from a hydrocarbon, and such hydrocarbons include saturated or unsaturated aliphatic hydrocarbons, saturated or unsaturated alicyclic hydrocarbons, and aromatic hydrocarbons.

[0083] (I-8) In the chemical structural formula showing the unit structure of the novolak resin in this specification, a bond (indicated by *) may be shown for convenience. However, unless otherwise specified, such a bond can be at any available bonding position in the unit structure, and does not in any way limit the bonding position in the unit structure.

[0084] Resin (G) Resin (G) has a complex unit structure, which includes a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms.

[0085] The composite unit structure of the resin (G) is represented, for example, by the following formula (AB). (In formula (AB), A represents the unit structure (A), and B represents the unit structure (B).)

[0086] --A-1: Unit structure (A)-- The unit structure (A) has an aromatic ring. The unit structure (A) has, for example, at least one of an oxygen atom constituting the aromatic ring, a sulfur atom constituting the aromatic ring, an oxygen atom bonded to the aromatic ring, a nitrogen atom constituting the aromatic ring, and a nitrogen atom directly bonded to the aromatic ring. The unit structure (A) does not have a heteroatom, for example, as an atom constituting the aromatic ring or an atom bonded to the aromatic ring.

[0087] The number of carbon atoms contained in the unit structure (A) is not particularly limited, but is, for example, 4 to 100, and preferably 4 to 50.

[0088] Preferably, such aromatic rings have from 4 to 30, more preferably from 4 to 24, carbon atoms.

[0089] Preferably, such aromatic ring is one or more benzene rings, naphthalene rings, anthracene rings, or pyrene rings; or a condensed ring of a benzene ring, a naphthalene ring, an anthracene ring, or a pyrene ring with a heterocycle or an aliphatic ring (such as a fluorene ring, a benzofluorene ring, a dibenzofluorene ring, an indole ring, a carbazole ring, or an indolocarbazole ring).

[0090] The aromatic ring may have any substituent, and from the viewpoint of polymerization reactivity, the substituent may contain the minimum necessary number of heteroatoms.In addition, the aromatic ring may have two or more aromatic rings connected by a linking group, and the linking group may contain the minimum necessary number of heteroatoms.Examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, etc.

[0091] The "aromatic ring" may contain at least one heteroatom selected from N, S and O on, within or between the rings.

[0092] Examples of heteroatoms that may be contained on the ring include nitrogen atoms contained in amino groups (e.g., propargylamino groups) and cyano groups; oxygen atoms contained in oxygen-containing substituents such as formyl groups, hydroxy groups, carboxyl groups, alkoxy groups, alkenyloxy groups, alkynyloxy groups (e.g., propargyloxy groups), and aryloxy groups; and nitrogen atoms and oxygen atoms contained in nitro groups, which are oxygen-containing and nitrogen-containing substituents. Examples of heteroatoms that may be contained in the ring include oxygen atoms contained in furan and xanthene, nitrogen atoms contained in carbazole and pyrrole, and sulfur atoms contained in phenothiazine. Examples of heteroatoms that may be contained in the linking group of two or more aromatic rings include -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, and -SO ２ Examples of the aromatic ring include a nitrogen atom, an oxygen atom, and a sulfur atom. In this specification, "an atom constituting an aromatic ring" is synonymous with "an atom contained within the ring." "An atom bonded to an aromatic ring" refers to, for example, "an atom directly bonded to the ring among atoms or groups contained on the ring" and "an atom directly bonded to the ring among atoms contained between rings." For example, the atoms constituting a benzene ring are carbon atoms. For example, the atoms constituting a pyrrole ring are carbon atoms and nitrogen atoms. For example, the oxygen atom of a hydroxyl group in phenol is not an atom constituting an aromatic ring. For example, the oxygen atom of a hydroxyl group in phenol is an atom bonded to the benzene ring, and is an atom directly bonded to the benzene ring among groups contained on the benzene ring.

[0093] ---A-2: Examples of skeletons constituting the unit structure (A)--- The unit structure (A) has, for example, a skeleton having an aromatic ring.

[0094] The skeleton having an aromatic ring is a phenol skeleton.

[0095] The unit structure (A) is, for example, a residue obtained by removing two hydrogen atoms from a skeleton having an aromatic ring. The skeleton having an aromatic ring is derived, for example, from a compound having an aromatic ring when synthesizing the resin (G). The skeleton having an aromatic ring is, for example, a residue obtained by removing two hydrogen atoms from a compound having an aromatic ring when synthesizing the resin (G).

[0096] The skeleton having an aromatic ring may have a substituent.

[0097] ---A-2-3: Phenol Skeleton--- The phenol skeleton refers to a skeleton having an aromatic ring and a hydroxy group bonded to the aromatic ring. The number of hydroxy groups bonded to the aromatic ring of the phenol skeleton is not particularly limited and may be one or more. When there are more than one hydroxy groups, the number may be 2 to 10 or 2 to 8. When there are more than one hydroxy groups, the hydroxy groups may be bonded to the same aromatic ring (e.g., a benzene ring) or to different aromatic rings. As will be described later, in the unit structure (A), the hydrogen atom of the hydroxy group bonded to the aromatic ring may be replaced with a substituent.

[0098] Examples of the phenol skeleton include skeletons represented by the following formula (A-4). (In the formula, n1, n2, n4, n5, n6, and n9 each independently represent an integer of 1 to 4. n3a, n3b, n7a, n7b, n8a, and n8b each independently represent an integer of 0 to 4, provided that the sum of n3a and n3b ​​is 1 or more, the sum of n7a and n7b is 1 or more, and the sum of n8a and n8b is 1 or more.)

[0099] Examples of the phenol skeleton include skeletons represented by the following formula (A-5a) or formula (A-5d). (In the formula, Ar ４１ each independently represents a residue of an aromatic ring. １ is -O-, -S-, -SO ２ - or an alkylene group which may be substituted with a halogen atom. ２ each independently represents a single bond, —O—, —S—, or —SO２ Y represents - or an alkylene group which may be substituted with a halogen atom. １ represents a trivalent saturated hydrocarbon group. ２ represents a tetravalent saturated hydrocarbon group. m1 and m2 each independently represent an integer of 0 to 3, provided that the sum of m1 and m2 is 1 or more. m3 to m5 each independently represent an integer of 0 to 3, provided that the sum of m3 to m5 is 1 or more. m6 to m8 each independently represent an integer of 0 to 3, provided that the sum of m6 to m8 is 1 or more. m9 to m12 each independently represent an integer of 0 to 3, provided that the sum of m9 to m12 is 1 or more.

[0100] Ar ４１ Examples of the aromatic ring in the residue of the aromatic ring include aromatic rings represented by the following formula (G3).

[0101] X １ , and X ２ The number of carbon atoms in the alkylene group which may be substituted with a halogen atom in the formula (I) is, for example, 1 to 20. The structure of the alkylene group may be, for example, linear, branched, cyclic, or a combination of two or more thereof. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0102] Y １ , and Y ２ The number of carbon atoms in the saturated hydrocarbon group in the formula (I) is, for example, 1 to 20. The structure of the saturated hydrocarbon group may be, for example, linear, branched, or cyclic, or a combination of two or more thereof.

[0103] Examples of the phenol skeleton include skeletons represented by the following formula (A-6a), (A-6b-1), (A-6b-2), (A-6c), or (A-6d). (In formula (A-6a), formula (A-6b-1), formula (A-6b-2), formula (A-6c), and formula (A-6d), Ar ５１each independently represents a residue of an aromatic ring. Each n11 independently represents an integer of 1 to 4. Each p independently represents 0 or 1. When p is 1, the oxygen atom forms an ether bond to bridge the aromatic rings, and when p is 0, there is no ether bond to form a bridge between the aromatic rings. L represents a single bond or a divalent linking group.

[0104] Ar ５１ Examples of the aromatic ring in the formula (G1) include aromatic rings represented by the following formula (G1), and a benzene ring and a naphthalene ring are preferred.

[0105] Examples of L include divalent groups obtained by removing two hydrogen atoms from the following structures:

[0106] For example, n11 each independently represents 1 or 2.

[0107] Examples of the phenol skeleton include skeletons represented by the following formula (A-7a), (A-7b), or (A-7c). (In formula (A-7a), formula (A-7b), and formula (A-7c), Ar ６１ each independently represents a residue of an aromatic ring; and each n21 independently represents an integer of 1 to 4.

[0108] Ar ６１ Examples of the aromatic ring in the formula (G1) include aromatic rings represented by the above formula (G1), and a benzene ring and a naphthalene ring are preferred. n21 each independently represents 1 or 2, for example.

[0109] Furthermore, examples of the phenol skeleton include skeletons represented by the following formula (A-8a-1), (A-8a-2), (A-8b), (A-8c), (A-8d), (A-8e), (A-8f), (A-8g-1), or (A-8g-2). In formula (A-8a-1), formula (A-8b), formula (A-8c), formula (A-8e), formula (A-8f), formula (A-8g-1), and formula (A-8g-2), n31 each independently represents an integer of 1 to 4. In formula (A-8a-2), n32 and n33 each independently represent an integer of 0 to 4, provided that the sum of n32 and n33 is 1 or more. In formula (A-8d), n32 and n33 each independently represent an integer of 0 to 4, provided that the sum of n32 and n33 is 1 or more. In formula (A-8b), X １ represents —O— or —NH—. ２ represents —O— or —S—. ３ is -S-, -CH ２ In formula (A-8f), X represents - or -NH-. ４ represents —CO— or —O—, and X ５ is -CH ２ represents - or -O-.)

[0110] For example, n31 each independently represents 1 or 2. n32 and n33 each independently represents 0, 1 or 2.

[0111] Examples of the skeleton represented by formula (A-4) include the following skeletons:

[0112] Examples of the skeleton represented by formula (A-5a) include the following skeletons:

[0113] Examples of the skeleton represented by formula (A-5b) include the following skeletons:

[0114] Examples of the skeleton represented by formula (A-5c) include the following skeletons:

[0115] Examples of the skeleton represented by formula (A-5d) include the following skeletons:

[0116] Examples of the skeleton represented by formula (A-6a) include the following skeletons:

[0117] Examples of the skeleton represented by formula (A-6b-1) or formula (A-6b-2) include the following skeletons:

[0118] Examples of the skeleton represented by formula (A-6c) include the following skeletons:

[0119] Examples of the skeleton represented by formula (A-6d) include the following skeletons:

[0120] Examples of the skeleton represented by formula (A-7a), formula (A-7b), or formula (A-7c) include the following skeletons.

[0121] Examples of the skeleton represented by formula (A-8a-1) or formula (A-8a-2) include the following skeletons:

[0122] Examples of the skeleton represented by formula (A-8b) include the following skeletons:

[0123] Examples of the skeleton represented by formula (A-8c) include the following skeletons:

[0124] Examples of the skeleton represented by formula (A-8d) include the following skeletons:

[0125] Examples of the skeleton represented by formula (A-8e) include the following skeletons:

[0126] Examples of the skeleton represented by formula (A-8f) include the following skeletons:

[0127] Examples of the skeleton represented by formula (A-8g-1) or formula (A-8g-2) include the following skeletons.

[0128] Examples of other skeletons besides the phenol skeleton include the following skeletons.

[0129] Furthermore, H of a hydroxy group bonded to the aromatic ring in the skeleton having the aromatic ring and a hydrogen atom bonded to the aromatic ring in the skeleton having the aromatic ring may be replaced with a substituent. Examples of the substituent include the substituents (S) represented by the following formulae (S1) to (S7).

[0130] (In formulas (S1) to (S7), R ｓａ represents a monovalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms. ｓｂ R each independently represents a single bond or a divalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms. ｓｃ R each independently represents a divalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms. ｓｄ ａｌｋｙｎｙｌ each independently represents an alkynyl group having 2 to 4 carbon atoms. ｓａ each independently represents a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. ｓｂ each independently represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. ｓａ and X ｓｂ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or X ｓａ and X ｓｂ together with the carbon atom bonded to the hydroxy group, form a carbonyl group. n represents an integer of 0 to 5. * represents a bond.

[0131] <R ｓａ > R ｓａExamples of the monovalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms in the formula (I) include an alkyl group having 1 to 10 carbon atoms and a monovalent unsaturated hydrocarbon group having 2 to 10 carbon atoms. The monovalent unsaturated hydrocarbon group having 2 to 10 carbon atoms has one or more carbon-carbon multiple bonds. When the monovalent unsaturated hydrocarbon group having 2 to 10 carbon atoms has two or more carbon-carbon multiple bonds, the two or more carbon-carbon multiple bonds may all be carbon-carbon double bonds, all may be carbon-carbon triple bonds, or may be a mixture of carbon-carbon double bonds and carbon-carbon triple bonds. The two or more carbon-carbon multiple bonds may or may not be conjugated.

[0132] <R ｓｂ , and R ｓｃ > R ｓｂ , and R ｓｃ In the formula, examples of the divalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms include an alkylene group having 1 to 10 carbon atoms and a divalent unsaturated hydrocarbon group having 2 to 10 carbon atoms. The divalent unsaturated hydrocarbon group having 2 to 10 carbon atoms has one or more carbon-carbon multiple bonds. When the divalent unsaturated hydrocarbon group having 2 to 10 carbon atoms has two or more carbon-carbon multiple bonds, the two or more carbon-carbon multiple bonds may all be carbon-carbon double bonds, all may be carbon-carbon triple bonds, or may be a mixture of carbon-carbon double bonds and carbon-carbon triple bonds. The two or more carbon-carbon multiple bonds may or may not be conjugated. R ｓｂ , and R ｓｃ Examples of the group include the following groups: (* represents a bond.)

[0133] <R ｓｄ ａｌｋｙｎｙｌ > R ｓｄ ａｌｋｙｎｙｌ represents an alkynyl group having 2 to 4 carbon atoms. Examples of the alkynyl group having 2 to 4 carbon atoms include an ethenyl group, a 1-propynyl group, and a propargyl group (2-propynyl group).

[0134] <Ar ｓａ > Ar ｓａThe monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms in the formula (I) is a residue obtained by removing one hydrogen atom from an aromatic hydrocarbon having 6 to 20 carbon atoms. Examples of aromatic hydrocarbons having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, perinaphthane, pyrene, fluorene, and biphenyl.

[0135] <Ar ｓｂ > Ar ｓｂ The divalent aromatic hydrocarbon group having 6 to 20 carbon atoms in the formula (I) is a residue obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 20 carbon atoms. Examples of aromatic hydrocarbons having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, and biphenyl.

[0136] <X ｓａ and X ｓｂ > X ｓａ and X ｓｂ In the formula (I), examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a monovalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms and a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Examples of the monovalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms include an alkyl group having 1 to 10 carbon atoms. A monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms is a residue obtained by removing one hydrogen atom from an aromatic hydrocarbon having 6 to 20 carbon atoms. Examples of aromatic hydrocarbons having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, perinaphthane, pyrene, fluorene, and biphenyl.

[0137] Examples of the substituent represented by formula (S1) include the following groups. (* represents a bond.)

[0138] Examples of the substituent represented by formula (S2) include the following groups. (* represents a bond.)

[0139] Examples of the substituent represented by formula (S3) include the following groups. (* represents a bond.)

[0140] Examples of the substituent represented by formula (S4) include the following groups. (* represents a bond.)

[0141] Examples of the substituent represented by formula (S5) include the following groups. (* represents a bond.)

[0142] Examples of the substituent represented by formula (S6) include the following groups. (* represents a bond.)

[0143] Examples of the substituent represented by formula (S7) include the following groups. (* represents a bond.)

[0144] Examples of other substituents include the following groups: (* represents a bond.)

[0145] The unit structure (A) is preferably at least one selected from the following: Note that the positions of the two bonds shown in each unit structure shown below are shown merely for convenience, and each bond can extend from any possible carbon atom, and the positions are not limited thereto.

[0146] (Example of a unit structure composed of a phenol skeleton)

[0147] --B-1: Unit structure (B)-- The unit structure (B) has one or more carbon atoms. The unit structure (B) is, for example, a unit structure derived from an aldehyde compound or an aldehyde equivalent. The unit structure (B) is one or more types of unit structures containing a linking carbon atom bonding to an aromatic ring in the unit structure (A) [see (I-1) above], and includes, for example, a structure represented by the formula (B1), (B2), or (B3) shown below. The unit structure (B) can link two unit structures (A) by forming a covalent bond with the unit structure (A).

[0148] ---B-2: Formula (B1)--- The unit structure (B) includes, for example, a structure represented by the following formula (B1): The unit structure (B) may be a structure represented by the following formula (B1). In formula (B1), R and R' each independently represent a hydrogen atom, an aromatic ring having 6 to 30 carbon atoms which may have a substituent, a heterocyclic ring having 3 to 30 carbon atoms which may have a substituent, or a linear, branched, or cyclic alkyl group having 10 or less carbon atoms which may have a substituent. R and R' may form a structure having a ring structure together with the carbon atom to which they are bonded. * represents a bond.

[0149] Examples of the substituent include a hydroxy group, a carboxy group, a formyl group, a nitro group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, and a group in which the H of a hydroxy group has been substituted with the above-mentioned substituent (S).

[0150] Furthermore, the two bonds in formula (B1) can be covalently bonded to the aromatic rings in the two structural units (A), respectively.

[0151] In the definitions of R and R' in formula (B1), the "aromatic ring" and "heterocycle" can be seen in (I-3) and (I-4) above.

[0152] In the definition of R and R′ in formula (B1), examples of the “alkyl group” include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1- Ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group ethyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group cyclobutyl group, 3-ethylcyclobutyl group, 1,2-dimethylcyclobutyl group, 1,3-dimethylcyclobutyl group, 2,2-dimethylcyclobutyl group, 2,3-dimethylcyclobutyl group, 2,4-dimethylcyclobutyl group, 3,3-dimethylcyclobutyl group, 1-n-propylcyclopropyl group, 2-n-propylcyclopropyl group, 1-i-propylcyclopropyl group, 2-i-propylcyclopropyl group, 1,2,2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,Examples include a 3-trimethyl-cyclopropyl group, a 1-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-1-methyl-cyclopropyl group, a 2-ethyl-2-methyl-cyclopropyl group, and a 2-ethyl-3-methyl-cyclopropyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.

[0153] Preferably, R and R' are each independently phenyl, naphthalenyl, anthracenyl, phenanthrenyl, naphthacenyl, or pyrenyl.

[0154] Examples of the ring structure formed by R and R' together with the carbon atoms to which they are bonded include structures represented by the following formulas. (In the formula, each Ar independently represents a residue of an aromatic ring. The carbon atom marked with * is the carbon atom bonded to R and R′ in formula (B1).)

[0155] Examples of the aromatic ring of Ar include aromatic rings represented by formula (G1).

[0156] The unit structure (B) containing the structure represented by formula (B1) is derived from, for example, an aldehyde compound or a ketone compound. Examples of the aldehyde compound include the compound represented by the following formula (B-1a). Examples of the ketone compound include the compound represented by the following formula (B-1b). (In formula (B-1a) and formula (B-1b), R and R' have the same meanings as R and R' in formula (B1), respectively, with the proviso that R is other than a hydrogen atom. In formula (B-1b), R and R' may form a structure having a ring structure together with the carbon atom to which they are bonded.)

[0157] For example, in obtaining resin (G), the carbonyl groups in formula (B-1a) and formula (B-1b) are converted to *-C-* in formula (B1).

[0158] Some specific examples of the unit structure (B) containing the structure represented by formula (B1) are as follows. * basically indicates the bonding site with the unit structure (A). Needless to say, the structure may contain the exemplified structure as a part of the whole.

[0159]

[0160] ---B-3: Formula (B2)--- The unit structure (B) includes, for example, a structure represented by the following formula (B2): The unit structure (B) may be a structure represented by the following formula (B2).

[0161] In formula (B2), Z ０ represents an aromatic ring residue or aliphatic ring residue having 6 to 30 carbon atoms, which may have a substituent, or an organic group in which two aromatic or aliphatic rings are linked by a single bond. Examples of the organic group in which two aromatic or aliphatic rings are linked by a single bond include divalent residues such as biphenyl, cyclohexylphenyl, and bicyclohexyl.

[0162] Examples of the substituent include a hydroxy group, a carboxy group, a formyl group, a nitro group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, and a group in which the H of a hydroxy group has been substituted with the above-mentioned substituent (S).

[0163] J １ and J ２ each independently represents a divalent organic group which may have a direct bond or a substituent. The divalent organic group is preferably a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, an aryl group (e.g., a phenyl group, a substituted phenyl group), or a halo group (e.g., fluorine) as a substituent. Examples of linear alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.

[0164] The unit structure (B) containing the structure represented by formula (B2) is derived from, for example, a compound having a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom, a compound having a hydroxyl group, an alkoxy group, or a halo group bonded to the α-carbon atom (e.g., the benzylic carbon atom) of an alkylaryl group, or a compound having two carbon-carbon double bonds. These compounds are aldehyde equivalents.

[0165] Examples of compounds having a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom include compounds represented by the following formula (B-2a): Compounds having a hydroxyl group, an alkoxy group, or a halo group bonded to the α-carbon atom (such as the benzylic carbon atom) of an alkylaryl group include compounds represented by the following formula (B-2b): Compounds having two carbon-carbon double bonds include compounds represented by the following formula (B-2c) or (B-2d): (In formula (B-2a), formula (B-2b), and formula (B-2b), J １ , J ２ , and Z ０ is J in formula (B2) １ , J ２ , and Z ０ In formula (B-2a), X ａ , and X ｂ each independently represents a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom. ａ , and Y ｂ each independently represents a hydroxyl group, an alkoxy group, or a halo group bonded to the α-position carbon atom (e.g., the benzyl-position carbon atom) of the alkylaryl group. In formula (B-2d), n represents an integer of 0 to 4.

[0166] For example, when obtaining resin (G), X in formula (B-2a) ａ -J １ is *-J in formula (B2). １ It is converted into ２ -X ｂ is J in formula (B2) ２For example, when resin (G) is obtained, Y in formula (B-2b) is converted to -*. ａ -J １ is *-J in formula (B2). １ It is converted into ２ -Y ｂ is J in formula (B2) ２ It is converted to -*.

[0167] An example of formula (B-2a) is the following compound:

[0168] An example of formula (B-2b) is the following compound:

[0169] An example of formula (B-2c) is the following compound:

[0170] Some specific examples of unit structures containing the structure represented by formula (B2) are as follows: * indicates the bonding site with unit structure A. Needless to say, the unit structure may contain the exemplified structure as a part of the whole.

[0171]

[0172] ---B-4: Formula (B3) --- In formula (B3), Z is a group having a monocyclic ring or a bicyclic, tricyclic, or tetracyclic fused ring, which may have a substituent, and which has 4 to 25 carbon atoms. The number of carbon atoms referred to here means only the number of carbon atoms constituting the ring skeleton of the monocyclic ring or the bicyclic, tricyclic, or tetracyclic fused ring excluding the substituent, and does not include the number of heteroatoms constituting the heterocyclic ring when the monocyclic ring or the fused ring is a heterocyclic ring.

[0173] The monocycle is a monocycle having a π electron number that does not satisfy 4n+2 (n is an integer of 0 or more) (hereinafter, may be referred to as a "non-Hückel monocycle"); at least one of the monocycles constituting the bicycle, tricycle, and tetracycle is a monocycle having a π electron number that does not satisfy 4n+2 (n is an integer of 0 or more), and the remaining monocycles may be either a monocycle having a π electron number that satisfies 4n+2 (n is an integer of 0 or more) or a monocycle having a π electron number that does not satisfy 4n+2 (n is an integer of 0 or more).

[0174] The monocyclic or bicyclic, tricyclic, or tetracyclic fused ring may further form a fused ring with one or more aromatic rings to form a pentacyclic or higher fused ring, and the pentacyclic or higher fused ring preferably has 40 or less carbon atoms. The number of carbon atoms referred to here means only the number of carbon atoms constituting the ring skeleton of the pentacyclic or higher fused ring excluding substituents, and does not include the number of heteroatoms constituting the heterocyclic ring when the pentacyclic or higher fused ring is a heterocyclic ring.

[0175] X and Y may be the same or different and each represent -CR ３１ R ３２ represents a - group, and R ３１ and R ３２ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

[0176] x and y represent the numbers X and Y, respectively, and each independently represents 0 or 1.

[0177] In formula (B3), and in formula (B3) At least one of the above is bonded to any carbon atom constituting the non-Hückel monocycle of Z (referred to as "carbon atom Z") (when x = 1, y = 1) or extends from carbon atom Z (when x = 0, y = 0).

[0178] For example, in formula (B3), is bonded to any carbon atom constituting the non-Hückel monocyclic ring of Z (referred to as "carbon atom 1") (when x = 1) or extends from carbon atom 1 (when x = 0),

[0179] In formula (B3), is bonded to any of the carbon atoms (referred to as "carbon atom 2") constituting the non-Hückel monocycle of Z (when y = 1) or extends from carbon atom 2 (when y = 0), and carbon atom 1 and carbon atom 2 may be the same or different, and if they are different, they may belong to the same non-Hückel monocycle or different non-Hückel monocycles.

[0180] Furthermore, formula (B3) may optionally contain linking carbon atoms other than carbon atom 1 and carbon atom 2. When Z is a tricyclic or higher fused ring, the permutation position relationship between one or two non-Hückel monocycles to which carbon atoms 1 and 2 in formula (B3) belong and the remaining monocycles in the fused ring is arbitrary, and when carbon atom 1 and carbon atom 2 belong to different non-Hückel monocycles (referred to as "non-Hückel monocycle 1" and "non-Hückel monocycle 2," respectively), the permutation position relationship between non-Hückel monocycle 1 and non-Hückel monocycle 2 in the fused ring is also arbitrary. Some specific examples of organic groups containing a structure represented by formula (B3) are as follows. The bonding site with unit structure A is not particularly limited. Needless to say, a structure containing the exemplified structure as a part of the whole may also be used.

[0181] Examples include those having more than two bonds (*), but these excess bonds can be used for bonding to an aromatic ring in another polymer chain, for crosslinking, or for other purposes, or they can be bonds to hydrogen bonds.

[0182]

[0183] Hereinafter, in formula (B3), and in formula (B3) In this case, only one of the carbon atoms constituting the non-Hückel monocycle of Z (referred to as "carbon atom Z") is bonded (when x = 1, y = 1) or extends from carbon atom Z (when x = 0, y = 0). As a more specific structure of formula (B3) in this case, for example, in the following formula (C31), p and k which can be bonding hands are １and k ２ Among them, p and k １ , or p and k ２ The remaining bond is bonded to a hydrogen atom.

[0184] In addition, in the following formula (C32), p and k which can be bonding hands １ , k ２ and m, p and k １ , p and k ２ , or depending on p and m, it can be a unit structure (B) represented by formula (B3). The remaining bond is bonded to a hydrogen atom.

[0185] Some specific examples of formula (B3) corresponding to formula (31) or formula (32) are as follows: * indicates the bonding site with the unit structure (A).

[0186] In formula (B3), a bond extends from the aromatic ring in each of these structures to another unit structure (for example, unit structure (A)), but in the specific examples below, such a bond is omitted. Needless to say, the unit structure may include the exemplified structure as a part of the whole. In the above specific examples, when there is no bond from the aromatic ring, it can be a specific example of a polymer terminal.

[0187] <<<<<Polymer (A4)>>>> Polymer (A4), which is an example of the organic compound (A), is a polymer having a unit structure represented by the following formula (Z1).

[0188] In the formula, A's each independently represent a hydrogen atom, a methyl group, or an ethyl group; １ and Q ２ are each independently a divalent group.

[0189] Q １ and Q ２ preferably, independently of one another, represent the formula (Z2) or the formula (Z3).

[0190]

[0191] In formula (Z2), Q ３ represents an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group, which may contain a sulfide bond or a disulfide bond. The phenylene group, naphthylene group, and anthrylene group may each independently be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. In formula (Z3), each B independently represents a single bond or an alkylene group having 1 to 5 carbon atoms. In formulas (Z2) and (3), * represents a bond. Each n independently represents 0 or 1. Each m independently represents 0 or 1. Each X is a group represented by formula (Z4), formula (Z5), or formula (Z6).

[0192]

[0193] In formula (Z4) and formula (Z5), R １ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group. The alkyl group and alkenyl group may be substituted with a halogen atom, a hydroxy group, or a cyano group. The benzyl group may have a hydrogen atom on the aromatic ring substituted with a hydroxy group. The phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms, and two R １ may be bonded to each other to form a ring having 3 to 6 carbon atoms. * represents a bond. *1 represents a bond bonded to a carbon atom in formula (Z3). *2 represents a bond bonded to a nitrogen atom in formula (Z3).

[0194] In formula (Z6), R ２represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group. The phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group, and an alkylthio group having 1 to 6 carbon atoms. *1 represents a bond bonding to a carbon atom in formula (Z3). *2 represents a bond bonding to a nitrogen atom in formula (Z3).

[0195] For example, Q １ and Q ２ At least one of them contains a structure represented by formula (Z3).

[0196] The alkylene group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include methylene, ethylene, propylene, pentamethylene, cyclohexylene, 2-methylpropylene, and 1-methylethylidene groups. Furthermore, the alkylene group having 1 to 10 carbon atoms and containing a sulfide bond or a disulfide bond includes alkylene groups containing a sulfide bond or a disulfide bond represented by the following formula:

[0197] (In the formula, * represents a bond.)

[0198] The alkenylene group having 2 to 10 carbon atoms may be straight-chain, branched or cyclic, and examples thereof include ethenylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene and nonenylene groups.

[0199] The alkyl group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, neopentyl, n-hexyl, cyclopentyl, and cyclohexyl groups.

[0200] The alkoxy group having 1 to 6 carbon atoms may be linear, branched or cyclic, and examples thereof include methoxy, ethoxy, i-propoxy, n-pentyloxy, n-hexyloxy and cyclohexyloxy groups.

[0201] The alkylthio group having 1 to 6 carbon atoms may be straight-chain, branched, or cyclic, and examples thereof include methylthio, ethylthio, i-propylthio, n-pentylthio, and cyclohexylthio groups.

[0202] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0203] Two R's １ Examples of the ring having 3 to 6 carbon atoms formed by bonding include a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

[0204] Examples of the unit structure represented by formula (Z1) include, but are not limited to, those represented by the following formulas (7) to (31). In the following formulas, Me is a methyl group. Furthermore, resin (A4) may have multiple types of unit structures represented by formula (Z1). For example, resin (A4) may have a unit structure represented by formula (7) and a unit structure represented by formula (32).

[0205]

[0206] [In the above formula, X represents a group represented by formula (Z4), formula (Z5), or formula (Z6), and R ６ and R ７ each independently represents an alkylene group having 1 to 3 carbon atoms or a direct bond, and p is the number of structural units and represents an integer of 5 to 100. [In the above formula, X represents a group represented by formula (Z4), formula (Z5), or formula (Z6), and R ６ and R ７ each independently represents an alkylene group having 1 to 3 carbon atoms or a direct bond; R ８ represents an alkylene group having 1 to 3 carbon atoms, m represents 0 or 1, and r represents the number of structural units and is an integer of 5 to 100.

[0207]

[0208]

[0209]

[0210]

[0211]

[0212] In the above formula (31), R is an alcohol residue (an organic group other than the hydroxyl group of an alcohol), and this R represents an alkyl group, an ether group, or a combination thereof. Examples of the R include an alkyl group and an alkoxyalkyl group. Examples of the alkyl group and the alkoxy group include those described above.

[0213] Compound (A5) Compound (A5), an example of the organic compound (A), is a compound having two or more of the following structure (M): (In structure (M), R １０１ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bond. The bond is bonded to, for example, a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring. R in structure (M) １０１ is a deprotectable protecting group, except when it is a hydrogen atom.

[0214] R １０１ is preferably a hydrogen atom, a methyl group, an ethyl group or a group represented by the following structure. (In the structure, R １０２ represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bond.

[0215] The compound (A5) is preferably a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, or a compound having a phenolic hydroxy group, which may be used alone or in combination of two or more.

[0216] Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been acyloxymethylated, or a mixture thereof.

[0217] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which one to four methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof; tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound in which one to four methylol groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof; and the like.

[0218] Examples of glycoluril compounds include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which one to four methylol groups of tetramethylol glycoluril are methoxymethylated or mixtures thereof, and compounds in which one to four methylol groups of tetramethylol glycoluril are acyloxymethylated or mixtures thereof.

[0219] The glycoluril compound may be, for example, a glycoluril derivative represented by the following formula (1E). (In formula (1E), four R １ each independently represents a methyl group or an ethyl group, R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

[0220] Examples of the glycoluril derivative represented by the formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0221] The glycoluril derivative represented by formula (1E) can be obtained, for example, by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0222] (In formula (2E), R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group; R ４ each independently represents an alkyl group having 1 to 4 carbon atoms.

[0223] (In formula (3d), R １ represents a methyl group or an ethyl group.

[0224] Examples of glycoluril derivatives represented by formula (2E) include compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include compounds represented by formulas (3d-1) and (3d-2) below.

[0225] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea compounds in which one to four methylol groups are methoxymethylated, or mixtures thereof, and tetramethoxyethyl urea.

[0226] Examples of the compound having a phenolic hydroxy group include compounds represented by the following formula (G-1) or (G-2). (In formula (G-1) and formula (G-2), Q １ represents a single bond or a monovalent organic group. １ and R ４ R represents an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. ２ and R ５ R represents a hydrogen atom or a methyl group. ３ and R ６n represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. １ is 1≦n １ an integer ≦3, n ２ is 2≦n ２ an integer ≦5, n ３ is 0≦n ３ an integer ≦3, n ４ is 0≦n ４ an integer ≦3, 3≦(n １ +n ２ +n ３ +n ４ ) represents an integer ≦6. ５ is 1≦n ５ an integer ≦3, n ６ is 1≦n ６ an integer ≦4, n ７ is 0≦n ７ an integer ≦3, n ８ is 0≦n ８ an integer ≦3, 2≦(n ５ +n ６ +n ７ +n ８ ) represents an integer of ≦5. m1 represents an integer of 2 to 10.

[0227] Examples of compounds having a phenolic hydroxy group include compounds represented by the following formula (G-3) or formula (G-4): The compound represented by formula (G-1) or formula (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or formula (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms. (In formula (G-3) and formula (G-4), Q ２ represents a single bond or a divalent organic group. ８ , R ９ , R １１ and R １２ R represents a hydrogen atom or a methyl group. ７ and R １０ n represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. ９ is 1≦n ９ an integer ≦3, n １０ is 2≦n １０ an integer ≦5, n１１ is 0≦n １１ an integer ≦3, n １２ is 0≦n １２ an integer ≦3, 3≦(n ９ +n １０ +n １１ +n １２ ) represents an integer ≦6. １３ is 1≦n １３ an integer ≦3, n １４ is 1≦n １４ an integer ≦4, n １５ is 0≦n １５ an integer ≦3, n １６ is 0≦n １６ an integer ≦3, 2≦(n １３ +n １４ +n １５ +n １６ ) represents an integer of ≦5. m2 represents an integer of 2 to 10. ２ In the above, the m2-valent organic group includes, for example, an m2-valent organic group having 1 to 4 carbon atoms.

[0228] Examples of the compound represented by formula (G-1) or formula (G-2) include the following compounds:

[0229] Examples of the compound represented by formula (G-3) or formula (G-4) include the following compounds: Me represents a methyl group. The above compound is available as a product of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. An example of the product is TMOM-BP, a product name of Asahi Organic Chemicals Co., Ltd.

[0230] The content of the organic compound (A) in the surface modifier is not particularly limited, but is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 5% by mass, and particularly preferably 0.1% by mass to 3% by mass.

[0231] <<<<Solvent (B)>>> The solvent (B) contained in the surface modifier can be any solvent that can dissolve and mix the organic compound (A) and, if necessary, other components contained in the surface modifier, without any particular limitation.

[0232] Examples of the solvent include organic solvents, water, etc. Examples of the organic solvent include alcohols, carboxylic acids having a hydroxy group, linear or cyclic alkyl ketones, cyclic lactones, alkylene glycol alkyl ethers, and alkylene glycol monoalkyl ether carboxylic acid esters (monocarboxylic acid esters of alkylene glycol monoalkyl ethers, and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers).

[0233] Examples of the alcohol include monoalcohol solvents and polyhydric alcohol solvents. Examples of the monoalcohol solvent include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, and n-octanol. Examples of polyhydric alcohol solvents include ethanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, etc. Examples of polyhydric alcohol solvents include ethylene glycol, propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, etc.

[0234] Examples of carboxylic acids having a hydroxy group include ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, and methyl 2-hydroxy-3-methylbutyrate.

[0235] Examples of linear or cyclic alkyl ketones include methyl ethyl ketone, cyclopentanone, and cyclohexanone.

[0236] An example of the cyclic lactone is γ-butyrolactone.

[0237] Examples of alkylene glycol alkyl ethers include alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers. Examples of alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl carbinol, and propylene glycol monobutyl ether. Examples of alkylene glycol dialkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether.

[0238] Examples of alkylene glycol monoalkyl ether carboxylic acid esters include monocarboxylic acid esters of alkylene glycol monoalkyl ethers and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers. Examples of monocarboxylic acid esters of alkylene glycol monoalkyl ethers include alkylene glycol monoalkyl ether acetates. Examples of alkylene glycol monoalkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate. Examples of the alkoxycarboxylic acid ester of alkylene glycol monoalkyl ether include 2-methoxyethyl methyl carbonate, 2-ethoxyethyl methyl carbonate, 2-ethoxyethyl ethyl carbonate, and 2-propoxyethyl methyl carbonate.

[0239] Specific examples of other solvents include toluene, xylene, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, and ethyl hydroxyacetate. Examples of suitable solvents include methyl 3-methoxy-2-methylpropionate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and 4-methyl-2-pentanol. These solvents can be used alone or in combination of two or more.

[0240] The surface modifier may contain water as a solvent. When water is contained as a solvent, the content of water can be, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less, based on the total mass of the solvents contained in the surface modifier.

[0241] <<<Acids, Salts Thereof, and Acid Generators; Compound (C)>>> The surface modifier may contain at least one compound (C) selected from the group consisting of acids, salts thereof, and acid generators. When the organic compound (A) has only hydroxy groups protected by deprotectable protecting groups as hydroxy groups, the surface modifier preferably contains compound (C). Examples of acids and salts thereof include hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, methanesulfonic acid, and salts thereof. As the acid generator, either a thermal acid generator or a photoacid generator can be used, but it is preferable to use a thermal acid generator. Examples of the thermal acid generator include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonate salt), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid.

[0242] Examples of the photoacid generator include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0243] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0244] Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0245] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0246] The concentration of the film-forming component in the surface modifier can be, for example, 0.01 to 50% by mass, 0.01 to 30% by mass, 0.01 to 25% by mass, or 0.01 to 20.0% by mass, relative to the total mass of the composition. The content of the organic compound (A) in the film-forming component is usually 20% by mass to 100% by mass, but from the viewpoint of reproducibly obtaining the effects of the present invention, the lower limit is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, and even more preferably 80% by mass, and the upper limit is preferably 100% by mass, with the remainder being the aforementioned additive. The film-forming component refers to the components in the surface modifier other than the solvent (B).

[0247] The surface modifier can be produced by mixing the organic compound (A), the solvent (B), and, if desired, other components. In this case, a solution containing the organic compound (A) may be prepared in advance, and this solution may be mixed with the solvent and other components. In preparing the surface modifier, heating may be performed as appropriate within a range that does not cause decomposition or deterioration of the components.

[0248] During the production of the surface modifier, or after all components have been mixed, the mixture may be filtered using a submicrometer filter or the like. The material of the filter used here is not critical, and examples that can be used include polyethylene filters, nylon filters, fluororesin filters, and polyimide filters.

[0249] <Second Step> The second step is a step of thinning the surface-modified layer precursor by bringing the surface-modified layer precursor into contact with a thinning liquid (X) to obtain a surface-modified layer having a film thickness of 5 nm or less.

[0250] In the second step, the method of contacting the surface-modified layer precursor with the thinning liquid (X) is not particularly limited, but spin coating is preferred because it allows uniform thinning and makes it easy to control the degree of thinning with high precision. That is, the second step is preferably a step of thinning the surface-modified layer precursor by spin-coating the thinning liquid (X) onto the surface-modified layer precursor to obtain a surface-modified layer with a film thickness of 5 nm or less.

[0251] The spin coating conditions are not particularly limited, but include, for example, a coating process in which a thinning liquid (X) is applied to a surface modification layer precursor formed on a semiconductor substrate, and a rotation process in which the semiconductor substrate is rotated. In the coating process, for example, when the thinning liquid (X) is applied to the surface modification layer precursor, the semiconductor substrate is not rotated or rotated at a low speed (e.g., 1000 rpm or less). In the coating process, the thinning liquid (X) is brought into contact with the surface modification layer precursor, and the components in the surface modification layer precursor are transferred to the thinning liquid (X). In the rotation process, for example, the semiconductor substrate is rotated at a high speed (e.g., greater than 1000 rpm and less than 5000 rpm), and the thinning liquid (X) is removed from the semiconductor substrate on which the surface modification layer precursor is formed. By doing so, the surface modification layer precursor becomes thinner by the amount of the components in the surface modification layer precursor transferred to the thinning liquid (X), resulting in a surface modification layer with a film thickness of 5 nm or less. The coating time may be, for example, 10 seconds to 2 minutes. The rotation time may be, for example, 5 seconds to 1 minute. During rotation, the axis perpendicular to the surface of the semiconductor substrate is used as the rotation axis.

[0252] In the second step, the film thickness of the surface modification layer precursor is preferably reduced by 0.5 nm to 10 nm, more preferably by 1 nm to 5 nm.

[0253] <<Thinning Liquid (X)>> The thinning liquid (X) is not particularly limited as long as it is a liquid that can thin the surface-modified layer precursor by contacting the surface-modified layer precursor with the thinning liquid (X), and examples thereof include organic solvents, water, acidic solutions, and alkaline aqueous solutions. Furthermore, thinners used in the RRC (reducing resist compression) process or the EBR (edge ​​bead removing) process can be used. These can be used alone or in combination of two or more.

[0254] Examples of the organic solvent include alcohol, alkylene glycol alkyl ether, and alkylene glycol monoalkyl ether carboxylic acid ester.

[0255] Examples of the alcohol include monoalcohol solvents and polyhydric alcohol solvents. Examples of the monoalcohol solvent include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, and n-octanol. Examples of the polyhydric alcohol solvent include ethanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, etc. Examples of the polyhydric alcohol solvent include ethylene glycol, propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, etc.

[0256] Examples of alkylene glycol alkyl ethers include alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers. Examples of alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl carbinol, and propylene glycol monobutyl ether. Examples of alkylene glycol dialkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether.

[0257] Examples of alkylene glycol monoalkyl ether carboxylic acid esters include alkylene glycol monoalkyl ether acetates, such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate.

[0258] Specific examples of other organic solvents include toluene, xylene, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, and butyl butyrate. Examples of suitable solvents include methyl acetoacetate, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxyisobutyrate, methyl 3-hydroxyisobutyrate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and 4-methyl-2-pentanol.

[0259] Examples of acidic solutions include inorganic acid aqueous solutions, organic acid aqueous solutions, and organic acid solutions. Examples of inorganic acid aqueous solutions include hydrochloric acid aqueous solutions, nitric acid aqueous solutions, phosphoric acid aqueous solutions, sulfuric acid aqueous solutions, and perchloric acid aqueous solutions. Examples of organic acid aqueous solutions include acetic acid aqueous solutions, trifluoroacetic acid aqueous solutions, camphorsulfonic acid aqueous solutions, p-toluenesulfonic acid aqueous solutions, and trifluoromethanesulfonic acid aqueous solutions. Examples of organic acid solutions include those in which the water in the above organic acid aqueous solutions has been replaced with an organic solvent. Examples of organic solvents include alkylene glycol alkyl ethers and alkylene glycol monoalkyl ether carboxylic acid esters.

[0260] Examples of alkaline aqueous solutions include developers used in lithography processes. Examples of alkaline aqueous solutions include inorganic alkaline aqueous solutions and organic alkaline aqueous solutions. Examples of inorganic alkaline aqueous solutions include potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium bicarbonate aqueous solution, potassium bicarbonate aqueous solution, sodium phosphate aqueous solution, and potassium phosphate aqueous solution. Examples of organic alkaline aqueous solutions include tetramethylammonium hydroxide aqueous solution, tetraethylammonium hydroxide aqueous solution, tetrabutylammonium hydroxide aqueous solution, monoethanolamine aqueous solution, diethanolamine aqueous solution, and triethanolamine aqueous solution. The concentration of alkali in the alkaline aqueous solution is not particularly limited.

[0261] The RRC (reducing resist consumption) process is a process for reducing the amount of photoresist used, in which a small amount of photoresist is uniformly applied over the entire surface of the substrate by treating the substrate surface with a thinner before applying the photoresist. The EBR (edge ​​bead removing) process is a process for removing unnecessary photoresist residue and other contaminants applied to the edge or rear surface of the substrate during the application process. Examples of thinners used in the RRC and EBR processes include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, cyclohexanone, ethyl lactate, γ-butyrolactone, ethyl 3-ethoxypropionate, methyl hydroxyisobutyrate, and mixtures thereof.

[0262] In one embodiment of the present invention, the laminate may include an organic underlayer film between the semiconductor substrate and the surface modification layer. The organic underlayer film used here is not particularly limited and can be selected from any of those commonly used in lithography processes. By providing an organic underlayer film on a substrate, a surface modification layer thereon, and a resist film (described below) on top of that, the pattern width of the resist film is narrowed. Even if the resist film is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas (described below). For example, the resist underlayer film can be processed using a fluorine-based gas having a sufficiently fast etching rate for the resist film as an etching gas. The organic underlayer film can also be processed using an oxygen-based gas having a sufficiently fast etching rate for the resist underlayer film as an etching gas. Furthermore, the substrate can be processed using a fluorine-based gas having a sufficiently fast etching rate for the organic underlayer film as an etching gas. The substrate and coating method that can be used in this case are the same as those described above.

[0263] (Method for manufacturing a semiconductor element) The method for manufacturing a semiconductor element of the present invention includes a step of forming a resist film on the laminate obtained by the method for manufacturing a laminate of the present invention, and a step of exposing and developing the resist film to obtain a resist pattern.

[0264] For example, a layer of a photoresist material (resist film) is formed on the surface modification layer. The resist film can be formed by a well-known method, i.e., by applying a coating-type resist material (resist film-forming composition) on the surface modification layer and baking it. The film thickness of the resist film is, for example, 10 nm to 10,000 nm, or 100 nm to 2,000 nm, or 200 nm to 1,000 nm, or 30 nm to 200 nm.

[0265] The photoresist material used in the resist film formed on the surface modification layer is not particularly limited as long as it is sensitive to the light used for exposure (e.g., KrF excimer laser, ArF excimer laser, etc.), and both negative and positive photoresist materials can be used. Examples include positive photoresist materials consisting of a novolac resin and a 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresist materials consisting of a binder having a group that decomposes in acid to increase the alkaline dissolution rate and a photoacid generator, chemically amplified photoresist materials consisting of a low molecular weight compound that decomposes in acid to increase the alkaline dissolution rate of the photoresist material, an alkali-soluble binder, and a photoacid generator, and chemically amplified photoresist materials consisting of a binder having a group that decomposes in acid to increase the alkaline dissolution rate, a low molecular weight compound that decomposes in acid to increase the alkaline dissolution rate of the photoresist material, and a photoacid generator. Specific examples of commercially available products include, but are not limited to, APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., AR2772JN (trade name) manufactured by JSR Corporation, and SEPR430 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. Other examples include fluorine-containing polymer photoresist materials such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0266] In addition, instead of a photoresist film, a resist film for electron beam lithography (also referred to as an electron beam resist film) or a resist film for EUV lithography (also referred to as an EUV resist film) can be used as the resist film formed on the surface modification layer. As the electron beam resist material for forming the electron beam resist film, either a negative or positive material can be used. Specific examples include a chemically amplified resist material comprising an acid generator and a binder having a group that decomposes in the presence of an acid to change the alkaline dissolution rate; a chemically amplified resist material comprising an alkali-soluble binder, an acid generator, and a low-molecular-weight compound that decomposes in the presence of an acid to change the alkaline dissolution rate of the resist material; a chemically amplified resist material comprising an acid generator, a binder having a group that decomposes in the presence of an acid to change the alkaline dissolution rate, and a low-molecular-weight compound that decomposes in the presence of an acid to change the alkaline dissolution rate of the resist material; a non-chemically amplified resist material comprising a binder having a group that decomposes in the presence of an electron beam to change the alkaline dissolution rate; and a non-chemically amplified resist material comprising a binder having a moiety that is cleaved by an electron beam to change the alkaline dissolution rate. When these electron beam resist materials are used, a resist film pattern can be formed in the same way as when a photoresist material is used with an electron beam as the irradiation source. Furthermore, as the EUV resist material for forming the EUV resist film, a methacrylate resin-based resist material, a polyhydroxystyrene resin-based resist material, and a methacrylate-polyhydroxystyrene hybrid resin-based resist material can be used.

[0267] The resist film may be a metal-containing resist film. The metal-containing resist film is not particularly limited, but preferably contains at least one element selected from the group consisting of Si, Ge, Sn, Ti, Zr, Hf, Al, and Co.

[0268] The metal-containing resist film is formed, for example, from a metal-containing resist. Metal-containing resists are also called metal oxide resists (MOR), and a representative example is a tin oxide-based resist. Examples of metal oxide resist materials include coating compositions containing metal oxo-hydroxo networks having organic ligands via metal-carbon bonds and / or metal carboxylate bonds, as described in JP 2019-113855 A. One example of a metal-containing resist uses a peroxo ligand as a radiation-sensitive stabilizing ligand. Details of peroxo-based metal oxo-hydroxo compounds are described, for example, in the patent document described in paragraph

[0011] of JP 2019-532489 A. Examples of such patent documents include U.S. Pat. No. 9,176,377 B2, U.S. Patent Application Publication No. 2013 / 0224652 A1, U.S. Pat. No. 9,310,684 B2, U.S. Patent Application Publication No. 2016 / 0116839 A1, and U.S. Patent Application Publication No. 15 / 291738. Other examples of metal-containing resists include those described in JP 2011-253185 A, WO 2015 / 026482, WO 2016 / 065120, WO 2017 / 066319, WO 2017 / 156388, WO 2018 / 031896, JP 2020-122959 A, JP 2020-122960 A, WO 2019 / 099981, WO 2019 / 199467, WO 2019 / 195522, WO 2019 / 195522, WO 2020 / 210660, WO 2021 / 011367, and WO 2021 / 016229. The contents of these are incorporated herein in their entirety to the same extent as if set forth in full.

[0269] The method for forming a metal-containing resist film from a metal-containing resist is not particularly limited, and examples include a method in which a coating-type resist material (a composition for forming a metal-containing resist film) that is a metal-containing resist is coated and baked.

[0270] The metal-containing resist film may also be formed by vapor deposition. Examples of methods for forming a metal-containing resist film by vapor deposition include the method described in JP 2017-116923 A. The contents of JP 2017-116923 A are incorporated herein by reference to the same extent as if fully set forth herein. In JP 2017-116923 A, the metal-containing resist film of the present invention is referred to as a metal oxide-containing film.

[0271] Next, the resist film formed on the surface modification layer is exposed to light through a predetermined mask (reticle). For the exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), or an F ２ Excimer laser (wavelength 157 nm), EUV (wavelength 13.5 nm), electron beam, etc. can be used. After exposure, post-exposure baking can be performed as needed. The post-exposure baking is performed under conditions appropriately selected from a heating temperature of 70°C to 150°C and a heating time of 0.3 minutes to 10 minutes.

[0272] Next, development is carried out using a developer (e.g., an alkaline developer). As a result, when a positive photoresist film is used, for example, the exposed portions of the photoresist film are removed, forming a photoresist film pattern. Examples of the developer (alkaline developer) include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like can also be added to these developers. Development conditions are appropriately selected from a temperature of 5 to 50°C and a time of 10 to 600 seconds.

[0273] In the present invention, an organic solvent can be used as a developer, and development is carried out with the developer (solvent) after exposure. As a result, when a negative photoresist film is used, for example, the photoresist film in the unexposed areas is removed, and a photoresist film pattern is formed. Examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 4-methyl ... Butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate,Examples of the developer include isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate. Furthermore, surfactants and the like can be added to these developers. The development conditions are appropriately selected from a temperature of 5°C to 50°C and a development time of 10 to 600 seconds.

[0274] For example, the surface modification layer is removed using the pattern of the resist film (upper layer) thus formed as a protective film, and then the substrate is processed using the patterned resist film and the patterned surface modification layer as protective films.

[0275] The removal (patterning) of the surface modification layer, which is performed using the pattern of the resist film (upper layer) as a protective film, is performed by, for example, dry etching using tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ Gases such as fluorine, trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane can be used. It is preferable to use a halogen-based gas for dry etching of the surface modification layer. Resist films (photoresist films) made of organic substances are generally difficult to remove with dry etching using a halogen-based gas. In contrast, surface modification layers containing a large amount of silicon atoms are quickly removed with a halogen-based gas. Therefore, it is possible to suppress the reduction in the thickness of the photoresist film that accompanies dry etching of the surface modification layer. As a result, it becomes possible to use a thin photoresist film. Therefore, it is preferable to use a fluorine-based gas for dry etching of the surface modification layer, and examples of the fluorine-based gas include tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F８ ), trifluoromethane, difluoromethane (CH ２ F ２ ) and the like, but are not limited to these.

[0276] The processing (patterning) of the (semiconductor) substrate using the patterned surface modification layer as a protective film is preferably performed by dry etching using a fluorine-based gas. Examples of the fluorine-based gas include tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, and difluoromethane (CH ２ F ２ ) etc.

[0277] After processing (patterning) the substrate, the surface modification layer can be removed. The removal of the surface modification layer can be performed by dry etching or wet etching. Dry etching of the surface modification layer is preferably performed using a fluorine-based gas, as mentioned in the patterning, such as tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, difluoromethane (CH ２ F ２ ) and the like. Chemical solutions used for wet etching of the surface modification layer include, but are not limited to, diluted hydrofluoric acid (hydrofluoric acid), buffered hydrofluoric acid (HF and NH ４Examples of suitable alkaline solutions include an aqueous solution containing hydrochloric acid and hydrogen peroxide (SC-2 chemical solution), an aqueous solution containing sulfuric acid and hydrogen peroxide (SPM chemical solution), an aqueous solution containing hydrofluoric acid and hydrogen peroxide (FPM chemical solution), and an aqueous solution containing ammonia and hydrogen peroxide (SC-1 chemical solution). Examples of alkaline solutions include the aforementioned ammonia hydrogen peroxide solution (SC-1 chemical solution) obtained by mixing ammonia, hydrogen peroxide, and water, as well as aqueous solutions containing 1 to 99% by mass of ammonia, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, 1-butyl-1-methylpyrrolidinium hydroxide, 1-propyl-1-methylpyrrolidinium hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide, mepicato hydroxide, trimethylsulfonium hydroxide, hydrazines, ethylenediamines, or guanidine. These chemical solutions can also be used in combination.

[0278] The present invention will be explained in more detail below with reference to synthesis examples and examples, but the present invention is not limited to the following examples.

[0279] In the examples, the apparatus and conditions used to analyze the physical properties of the samples are as follows. (1) Molecular Weight Measurement The molecular weight of the polymer used in the present invention is the molecular weight obtained by GPC analysis in terms of polystyrene. The GPC measurement conditions were a GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, tetrahydrofuran as eluent (elution solvent), a flow rate (flow rate) of 1.0 mL / min, and polystyrene (manufactured by Showa Denko K.K.). (2) AFM Observation A 10 μm x 10 μm area was observed using a Hitachi High-Technologies AFM 5500M, and the surface roughness was evaluated. (3) Film Thickness Measurement The film thickness of the material was measured using an ellipsometric film thickness measurement device RE-3100 (manufactured by SCREEN). The thickness of the surface modification layer precursor was measured as follows: ２ After measuring the thickness of the oxide film, a surface modifying agent was applied, and the thickness of the surface modified layer precursor was measured. The difference between the thicknesses was taken as the thickness of the surface modified layer precursor. The thickness of the surface modified layer was measured as follows. ２ After measuring the thickness of the oxide film, the surface modifier was applied to thin the film, and the thickness was then measured. The difference between the thicknesses was taken as the thickness of the surface-modified layer.

[0280] [1] Polymer Synthesis (Synthesis Example 1) 20.0 g of 2-hydroxyethyl methacrylate, 1.0 g of azobisisobutyronitrile, and 84.0 g of propylene glycol monomethyl ether were placed in a 500 mL flask and reacted at 60°C for 24 hours to obtain an acrylic polymer (vinyl polymer) solution (solids concentration 20% by mass). GPC analysis showed that the obtained acrylic polymer (vinyl polymer) had an Mw of 4,000 and an Mw / Mn of 1.6. The obtained acrylic polymer (vinyl polymer) had a unit structure represented by the following formula:

[0281] Synthesis Example 2 20.0 g of 2-hydroxypropyl methacrylate, 1.0 g of azobisisobutyronitrile, and 84.0 g of propylene glycol monomethyl ether were placed in a 500 mL flask and reacted at 60°C for 24 hours to obtain an acrylic polymer (vinyl polymer) solution (solids concentration 20% by mass). GPC analysis showed that the resulting acrylic polymer (vinyl polymer) had an Mw of 3,800 and an Mw / Mn of 1.7. The resulting acrylic polymer (vinyl polymer) had a unit structure represented by the following formula:

[0282] Synthesis Example 3 20.0 g of 4-hydroxystyrene, 1.0 g of azobisisobutyronitrile, and 84.0 g of propylene glycol monomethyl ether were placed in a 500 mL flask and reacted at 60°C for 24 hours to obtain a polymer (vinyl polymer) solution (solids concentration 20% by mass). GPC analysis showed that the obtained polymer (vinyl polymer) had an Mw of 2,500 and an Mw / Mn of 1.7. The obtained polymer (vinyl polymer) had a unit structure represented by the following formula:

[0283] Synthesis Example 4 40.0 g of epoxy resin (manufactured by Daicel Chemical Industries, Ltd., trade name: EHPE3150), 20.3 g of 9-anthracenecarboxylic acid, and 308.4 g of propylene glycol monomethyl ether were placed in a 500 mL flask and dissolved, and then 1.5 g of benzyltriethylammonium was added and the mixture was refluxed for 24 hours to allow the reaction to proceed. After the reaction, the solution was purified using an ion exchange method to obtain a polymer solution (solids concentration: 20% by mass). GPC analysis showed that the Mw of the obtained polymer was 4500. The obtained polymer had a unit structure represented by the following formula:

[0284] Synthesis Example 5 40.0 g of epoxy resin (manufactured by Daicel Chemical Industries, Ltd., trade name: EHPE3150), 20.3 g of 9-anthracenecarboxylic acid, 13.7 g of benzoic acid, and 302.0 g of propylene glycol monomethyl ether were placed in a 500 mL flask and dissolved, followed by addition of 1.5 g of benzyltriethylammonium and refluxing for 24 hours to allow reaction. After the reaction, the solution was purified using an ion exchange method to obtain a polymer solution (solids concentration: 20% by mass). GPC analysis showed that the Mw of the obtained polymer was 4100. The obtained polymer had a unit structure represented by the following formula:

[0285] Synthesis Example 6 70.0 g of 2,2'-biphenol, 86.6 g of 1-pyrenecarboxaldehyde, 10.8 g of methanesulfonic acid, and 167.4 g of propylene glycol monomethyl ether were placed in a 500 mL flask and reacted at 120°C for 24 hours. After the reaction, the solution was reprecipitated in 2500 g of methanol. The resulting precipitate was filtered and dried in a vacuum dryer at 50°C for 10 hours. The resulting solution was then redissolved in propylene glycol monomethyl ether to obtain a polymer solution (solids concentration 20% by mass). GPC analysis showed that the Mw of the resulting polymer was 1400 and the Mw / Mn was 1.5. The resulting polymer had a composite structural unit represented by the following formula:

[0286] Synthesis Example 7 7.5 g of 2,2'-biphenol, 12.6 g of 1-naphthaldehyde, 1.5 g of methanesulfonic acid, and 26.4 g of propylene glycol monomethyl ether were placed in a 100 mL flask and reacted at 120°C for 24 hours. After the reaction, the solution was reprecipitated in 2500 g of methanol. The resulting precipitate was filtered and dried in a vacuum dryer at 50°C for 10 hours. The resulting solution was then redissolved in propylene glycol monomethyl ether to obtain a polymer solution (solids concentration 20% by mass). GPC analysis showed that the Mw of the resulting polymer was 1690 and the Mw / Mn was 2.3. The resulting polymer had a composite unit structure represented by the following formula:

[0287] Synthesis Example 8 25.0 g of 2,2'-biphenol, 10.5 g of 1-naphthaldehyde, 15.5 g of 1-pyrenecarboxaldehyde, 3.8 g of methanesulfonic acid, and 54.8 g of propylene glycol monomethyl ether were placed in a 500 mL flask and reacted at 120°C for 24 hours. After the reaction, the solution was reprecipitated in 2500 g of methanol. The resulting precipitate was filtered and dried in a vacuum dryer at 50°C for 10 hours. The resulting solution was then redissolved in propylene glycol monomethyl ether to obtain a polymer solution (solids concentration: 20% by mass). GPC analysis showed that the Mw of the resulting polymer was 2000 and the Mw / Mn was 2.1. The resulting polymer had a composite unit structure represented by the following formula:

[0288] Synthesis Example 9 10.0 g of 1,6-bis(2,3-epoxypropan-1-yloxy)naphthalene, 5.1 g of 3,3'-dithiodipropionic acid, 0.7 g of ethyltriphenylphosphonium bromide, and 62.9 g of propylene glycol monomethyl ether were placed in a 500 mL flask and reacted at 105°C for 24 hours to obtain a polymer solution (solids concentration: 20% by mass). GPC analysis showed that the Mw of the obtained polymer was 3000 and the Mw / Mn was 1.4. The obtained polymer had a unit structure represented by the following formula:

[0289] Synthesis Example 10 15.00 g of 1,6-bis(2,3-epoxypropan-1-yloxy)naphthalene, 23.10 g of monoallyl diglycidyl isocyanurate, 31.72 g of 3,3'-dithiodipropionic acid, 2.55 g of ethyltriphenylphosphonium bromide, and 54.8 g of propylene glycol monomethyl ether were placed in a 500 mL flask and reacted at 105°C for 24 hours to obtain a polymer solution (solids concentration 20% by mass). GPC analysis showed that the Mw of the obtained polymer was 3300 and the Mw / Mn was 1.4. The obtained polymer had a unit structure represented by the following formula:

[0290] Comparative Synthesis Example 1 20.0 g of methyl methacrylate, 1.0 g of azobisisobutyronitrile, and 84.0 g of propylene glycol monomethyl ether were placed in a 500 mL flask and reacted at 60° C. for 24 hours to obtain an acrylic polymer solution (solids concentration: 20% by mass). GPC analysis showed that the Mw of the obtained acrylic polymer was 3,500 and the Mw / Mn was 1.4. The obtained acrylic polymer had a unit structure represented by the following formula:

[0291] Comparative Synthesis Example 2 6.69 g of carbazole, 7.28 g of 9-fluorenone, 0.76 g of paratoluenesulfonic acid monohydrate, and 6.69 g of 1,4-dioxane were placed in a 500 mL flask, and then a solution of 1,4-dioxane (manufactured by Kanto Chemical Co., Inc.) was added. The mixture was stirred and reacted at 100°C for 24 hours. After the reaction, the solution was diluted with 34 g of chloroform, and the diluted mixture was reprecipitated in 168 g of methanol. The resulting precipitate was filtered and dried in a vacuum dryer at 50°C for 10 hours. The resulting precipitate was then redissolved in propylene glycol monomethyl ether to obtain a polymer solution (solids concentration: 20% by mass). GPC analysis revealed that the Mw of the resulting polymer was 2,800 and the Mw / Mn was 1.8. The resulting polymer had a composite unit structure represented by the following formula:

[0292] [2] Preparation of Surface Modifier (Coating Liquid) The polymer obtained in the above Synthesis Example and the solvent were mixed in the proportions shown in Table 1, and the mixture was filtered through a 0.1 μm fluororesin filter to prepare the surface modifier (coating liquid). The amount of each additive in Tables 1-1 and 1-2 is shown in parts by mass. Note that the polymer was used in the preparation of the composition as the polymer solution obtained in the Synthesis Example, but the proportion of polymer added in Table 1 indicates the amount of polymer itself added, not the amount of polymer solution added.

[0293] The meanings of the abbreviations in Tables 1-1 and 1-2 are as follows: <Solvents> PGME: Propylene glycol monomethyl ether PGEE: Propylene glycol monoethyl ether PGMEA: Propylene glycol monomethyl ether acetate <Additives> Py-PTS: Pyridinium paratoluenesulfonate PL-LI: 1,3,4,6-tetrakis(methoxymethyl)tetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione TMOM-BP: 3,3',5,5'-tetrakis(methoxymethyl)-"1,1'-biphenyl"-4,4'-diol

[0294]

[0295]

[0296] [3] Thinning Test The prepared coating solutions 1 to 26 were each applied to a silicon wafer using a spinner. They were heated on a hot plate at an arbitrary temperature for 1 minute to form a surface modification layer precursor. A mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V): thinning solution) was then applied to each surface modification layer precursor and allowed to stand for 60 seconds. The wafer was then rotated to shake off the solvent, and the wafer was baked at 100 degrees for 30 seconds and dried. The thickness of the surface modification layer after application of the thinning solution was measured, and surface modifiers that reduced the film thickness to 30 Å or less and obtained a smooth surface as evaluated by AFM were rated "good," while those that showed uneven coating as evaluated by AFM were rated "uneven coating." The results are shown in Table 2.

[0297]

[0298] [4] Substrate Surface Modification Test Coating Solutions 1 to 26 were applied to bare-Si substrates. Specifically, using CLEANTRACK (registered trademark) ACT8 (Tokyo Electron), 1 ml of each of Coating Solutions 1 to 26 was applied to a wafer, spin-coated at 1500 rpm for 60 seconds, and then baked at the baking temperature listed in Table 3. A mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was then applied to each surface-modified layer precursor, followed by spin-drying to form a surface-modified layer with a thickness of 30 Å or less. The water contact angle was then measured for the bare-Si substrates on which the surface-modified layers of Coating Solutions 1 to 26 had been formed. The water contact angle was measured in a constant temperature and humidity environment (23°C ± 2°C, 45% RH ± 5%) using a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.) with a liquid volume of 3 μl, after the sample had been placed on the surface and left standing for 5 seconds before measurement. Since the water contact angle of Bare-Si was 20 degrees or less, a water contact angle of less than 30 degrees was deemed to be "poor" as the surface had not been modified, and a water contact angle of 30 degrees or more was deemed to be "good" as the surface had been modified. The measurement results are shown in Table 3 below.

[0299]

[0300] [5] Formation of Resist Pattern by EB Exposure Coating Solution 1 was spin-coated onto bare silicon and heated at 215°C for 1 minute. A mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was then applied to the coating film, followed by spin drying to form a surface-modified layer (1-3 nm) with a thickness of 30 Å or less. An EUV resist solution (methacrylate / PHS-based resist) was then spin-coated on top of the coating and heated at 110°C for 1 minute to form an EUV resist film (C layer). This was then exposed using an Elionix EB lithography system (ELS-G130). After exposure, post-exposure baking (PEB, 90°C for 1 minute) was performed, followed by cooling to room temperature on a cooling plate. The resist was then developed for 30 seconds using a 2.38% TMAH developer and rinsed to form a resist pattern. Using the same procedure, resist patterns were formed using substrates having surface-modified layers obtained from each of Coating Solutions 2 to 26. Furthermore, as Comparative Example 13, a resist pattern was formed on a bare-Si wafer that was not coated with a surface modifier. The heating temperature (baking temperature) after spin-coating the coating solution was the baking temperature shown in Table 4. The resulting patterns were evaluated for the formation of a 50 nm pitch, 25 nm line pattern by observing the pattern cross section. In observing the pattern shape, a state in which the shape was between footing and undercut and there was no significant residue in the space was evaluated as "good," and an undesirable state in which the resist pattern collapsed was evaluated as "collapse." The results are shown in Table 4.

[0301]

Claims

1. A method for producing a laminate having a surface modification layer and a semiconductor substrate, comprising: a first step of applying a surface modification agent containing an organic compound (A) having a hydroxyl group which may be protected by a deprotectable protecting group and a solvent (B) onto a semiconductor substrate, followed by baking to obtain a surface modification layer precursor; and a second step of contacting the surface modification layer precursor with a thinning liquid (X) to thin the surface modification layer precursor to obtain a surface modification layer having a thickness of 5 nm or less.

2. The method for producing a laminate according to claim 1, wherein the organic compound (A) is any one of: a vinyl polymer (A1) having a hydroxyl group; a polymer (A2) having a unit structure represented by the following formula (Y); a resin (A3) having a complex unit structure, the complex unit structure having a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms, and obtained by a reaction to form a covalent bond between a carbon atom constituting the aromatic ring of the unit structure (A) and a carbon atom in the unit structure (B); a polymer (A4) having a unit structure represented by the following formula (Z1); and a compound (A5) having two or more of the following structures (M). In formula (Y), T represents a divalent group having an aliphatic ring. Q represents a divalent organic group having a hydroxyl group. １１ R represents a divalent organic group connecting １１ represents a monovalent group. In formula (Z1), A's each independently represent a hydrogen atom, a methyl group, or an ethyl group; １ and Q. ２ each independently represents a divalent group. (In structure (M), R １０１ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bond.

3. The method for producing a laminate according to claim 1, wherein the solvent (B) contains at least one member selected from the group consisting of a carboxylic acid having a hydroxy group, a linear or cyclic alkyl ketone, a cyclic lactone, an alkylene glycol monoalkyl ether, a monocarboxylic acid ester of an alkylene glycol monoalkyl ether, and an alkoxycarboxylic acid ester of an alkylene glycol monoalkyl ether.

4. The method for producing a laminate according to claim 1, wherein the thinning liquid (X) contains at least one of an organic solvent and water.

5. The method for producing a laminate according to claim 1, wherein the surface modifier further comprises at least one compound (C) selected from the group consisting of acids, their salts, and acid generators.

6. The method for producing a laminate according to claim 1, wherein the semiconductor substrate is an inorganic or organic substrate, or a substrate having an inorganic or organic film.

7. The method for producing a laminate according to claim 6, wherein the inorganic material is at least one selected from the group consisting of metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxycarbides, and metal carbonitrides.

8. The method for producing a laminate according to claim 6, wherein the organic material is at least one selected from the group consisting of amorphous carbon, graphite, fullerene, carbon nanotube, diamond, diamond-like carbon, polyimide, and organic films doped or partially substituted with boron, oxygen, nitrogen, phosphorus, silicon, sulfur, or a halogen.

9. The method for producing a laminate according to claim 1, wherein the laminate further comprises a resist underlayer film.

10. A method for producing a laminate as described in claim 1, wherein the second step is a step of thinning the surface modification layer precursor by spin-coating the thinning liquid (X) onto the surface modification layer precursor to obtain a surface modification layer having a film thickness of 5 nm or less.

11. The method for producing a laminate according to claim 1, wherein the laminate is used for EUV or electron beam lithography.

12. A method for manufacturing a semiconductor device, comprising the steps of: forming a resist film on a laminate obtained by the method for manufacturing a laminate according to any one of claims 1 to 11; and exposing and developing the resist film to obtain a resist pattern.

13. A laminate comprising a semiconductor substrate and a surface modification layer having a thickness of 5 nm or less formed using a surface modification agent containing an organic compound (A) having a hydroxyl group which may be protected by a deprotectable protecting group, and a solvent (B).

14. The laminate according to claim 13, which is used in EUV or electron beam lithography.

15. A surface modifier comprising an organic compound (A) having a hydroxyl group which may be protected by a deprotectable protecting group, and a solvent (B), the surface modifier being used in the method for producing a laminate according to any one of claims 1 to 11.

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